JP2004264807A - Method for forming color image - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a stable color image which exhibits little changes in the hue before and after consecutive processing without depending on the storage state of a silver halide photosensitive material. <P>SOLUTION: The photosensitive material in the method for forming an image includes: a yellow image forming unit containing a compound expressed by formula (1); a magenta image forming unit containing a compound expressed by formula (2); and a cyan image forming unit containing a compound expressed by formula (3). Thereby, a proof image having little changes in the hue before and after the consecutive development due to changes in the halftone dot percentage of secondary colors can be stably formed without depending on the storage state of the silver halide photosensitive material. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

【００６５】
【化９】

【００６６】
【化１０】

【００６７】
【化１１】

【００６８】
本発明に係るイエローカプラーは、通常、ハロゲン化銀乳剤層において、ハロゲン化銀１モル当たり１×１０^−３〜１モル、好ましくは１×１０^−２〜８×１０^−１モルの範囲で用いることができる。
【００６９】
請求項１に係る発明の特徴の一つは、前記一般式（ＩＩ）で表されるマゼンタカプラーを含有することにある。
【００７０】
以下に、前記一般式（ＩＩ）で表されるマゼンタカプラーについて説明する。
前記一般式（ＩＩ）において、Ｒ_２１で表される１級または２級アルキル基としては、メチル基、ｉｓｏ−プロピル基、２，２−ジメチルプロピル基などが好ましい。アリールアミノ基としては、アニリノ基等が好ましく、アルコキシ基としては、２−フェノキシエトキシ基などが好ましく用いられる。
【００７１】
Ｒ_２２で表される炭素原子数３以上の直鎖の連結基は、置換、無置換のトリメチレン基を挙げることができ、１，１−ジメチルプロピレン基等も好ましく用いることができる。
【００７２】
Ｒ_２３で表される耐拡散基としては、ドデシル基、ヘキサデシル基、オクタデシル基等の長鎖アルキル基または、アシルアミノ基で結合した耐拡散基が好ましく、例えば、パルミトイルアミノ、ステアロイルアミノ、２−（２，４−ジ−ｔ−ベンチルフェノキシ）ブタノイルアミノ基等の各基が挙げられる。
【００７３】
Ｊ_２で表される基の内、好ましいものは−（Ｃ＝Ｏ）−Ｏ−、−Ｏ−（Ｃ＝Ｏ）−、−（Ｃ＝Ｏ）−ＮＨ−、−ＮＨ−（Ｃ＝Ｏ）−、−Ｐｈ−（Ｃ＝Ｏ）−ＮＨ−、−Ｐｈ−ＮＨ−（Ｃ＝Ｏ）−であり、特に好ましくは−（Ｃ＝Ｏ）−Ｏ−、−（Ｃ＝Ｏ）−ＮＨ−である。
【００７４】
Ｒ_２４〜Ｒ_２７で表されるアルキル基は、炭素数１〜３２のものが好ましく、例えば、メチル基、エチル基、プロピル基、イソプロピル基、（ｔ）ブチル基、ヘキシル基、オクチル基、ドデシル基、ヘキサデシル基、２−エチルヘキシル基等がその代表例として挙げられる。
【００７５】
Ｒ_２４〜Ｒ_２７で表されるシクロアルキル基は、炭素数３〜１２のものが好ましく、例えば、シクロプロピル基、シクロペンチル基、シクロヘキシル基、２−メチルシクロプロピル基、アダマンチル基等がその代表例として挙げられる。
【００７６】
Ｒ_２４〜Ｒ_２７で表されるアリール基は、炭素数６〜１４のものが好ましく、その代表例としてはフェニル基、１−ナフチル基、２−ナフチル基等が挙げられる。
【００７７】
Ｒ_２４〜Ｒ_２７で表されるアルキル基、シクロアルキル基、アリール基は、各々置換基を有していてもよい。
【００７８】
Ｒ_２４〜Ｒ_２７で表される基としては、水素原子がより好ましく用いられる。
Ｘ_２は発色現像主薬の酸化体との反応により脱離可能な基を表すが、ハロゲン原子（例えば、塩素原子、臭素原子、弗素原子等）、アルコキシ基、アリールオキシ基、アルキルチオ基、アリールチオ基、複素環チオ基、Ｎ原子で結合した含窒素複素環（例えば、ヒダントイン核、オキサゾリジンジオン核、ウラゾール核等）が挙げられる。Ｒ_２１が１級または２級のアルキル基、アルコキシ基である場合は、Ｘ_２として、好ましくはハロゲン原子、特に好ましくは塩素原子であり、Ｒ_２１がアリールアミノ基である場合は、Ｘ_２としてアリールチオ基が好ましい。
【００７９】
以下に、前記一般式（ＩＩ）で表されるマゼンタカプラーの代表例を示すが、本発明はこれらに限定されるものではない。
【００８０】
【化１２】

【００８１】
【化１３】

【００８２】
【化１４】

【００８３】
【化１５】

【００８４】
【化１６】

【００８５】
一般式（ＩＩ）で表されるマゼンタカプラーは、本発明の効果を損なわない範囲において他の種類のマゼンタカプラーと併用することもでき、通常ハロゲン化銀１モル当たり１×１０^−３〜１モル、好ましくは１×１０^−２〜８×１０^−１モルの範囲で用いることができる。
【００８６】
本発明に係る感光材料において、形成されるマゼンタ画像の分光吸収のλ_ｍａｘは５３０〜５６０ｎｍであることが好ましく、またλＬ_０．２は、５８０〜６３５ｎｍであることが好ましい。
【００８７】
本発明に係るハロゲン化銀感光材料のマゼンタ画像形成層には、マゼンタカプラーに加えて、イエローカプラーが含有されることが好ましい。本発明に係るハロゲン化銀感光材料において、マゼンタ画像形成性層に含有させる好ましいイエローカプラーとしては、公知のピバロイルアセトアニリド型もしくはベンゾイルアセトアニリド型等のカプラーが挙げられる。本発明に係る感光材料のマゼンタ画像形成性層に含有させる好ましいイエローカプラーの具体例としては、特開平８−３１４０７９号の６〜１５ページ右欄に記載のＹＣＰ−１〜ＹＣＰ−３９で表されるカプラーが挙げられるが、もちろんこれらに限定されるものではない。
【００８８】
請求項１に係る発明の特徴の一つは、前記一般式（ＩＩＩ）〜一般式（ＶＩ）で表されるシアンカプラーから選ばれる少なくとも１種を含有することにある。以下に、前記一般式（ＩＩＩ）〜一般式（ＶＩ）で表されるシアンカプラーについて説明する。
【００８９】
前記一般式（ＩＩＩ）において、Ａｒはアリール基または複素環基を表し、アリール基としては、フェニル基またはナフチル基を挙げることができる。Ａｒで表される複素環基としては、５〜７員ものが好ましく、具体的には２−フリル基、２−チエニル基、２−ピリミジニル基、２−ベンゾチアゾリル基、１−ピロリル基、１−テトラゾニル基等を挙げることができる。
【００９０】
Ａｒで表されるアリール基、複素環基は、さらに置換基を有してもよく、これらの置換基としては、特に制限はないが、代表例としては、アルキル基、アルケニル基、アルキニル基、アリール基、複素環基を挙げることができる。Ａｒとして好ましくはフェニル基が挙げられる。
【００９１】
Ｒ_１はアルキル基、アルケニル基、アルキニル基、アリール基または複素環基を表し、Ｒ_１で表されるアルキル基としては、メチル基、エチル基、イソプロピル基、ブチル基、ドデシル基、シクロヘキシル基、アダマンチル基等を挙げることができる。アルキニル基としては、ビニル、アリル、オレイル、シクロヘキセニル基等が挙げられる。アルケニル基としては、プロパルギル、１−ペンチニル基等が挙げられる。Ｒ_１で表されるアリール基、Ｒ_１で表される複素環基としては、前記Ａｒで表される基と同義の基が挙げられる。Ｒ_１で表されるアルキル基、アルケニル基、アルキニル基、アリール基、複素環基は、更に置換基を有してもよい。
【００９２】
Ｌで表される２価の連結基としては、好ましくはアルキレン基、アリーレン基であり、ｎは０または１を表し、好ましくは０である。
【００９３】
前記一般式（ＩＶ）において、Ｒ_２、Ｒ_３、Ｒ_４で表されるアルキル基、アルケニル基、アルキニル基、アリール基または複素環基の代表例としては、一般式（ＩＩＩ）におけるＲ_１と同様の基を挙げることができる。Ｒ_２、Ｒ_３としては、好ましくはアルキル基、アリール基を挙げることができ、Ｒ_４は好ましくはアルキル基、アリール基であり、より好ましくはアルキル基であり、無置換アルキル基であるのが最も好ましい。
【００９４】
前記一般式（ＩＶ）において、Ｌは２価の連結基を表し、好ましくはアルキレン基、アリーレン基であり、ｎは０または１を表し、好ましくは０である。
【００９５】
前記一般式（Ｖ）において、Ｒ_５で表される炭素数５以上の無置換アルキル基、無置換アルケニル基、無置換アルキニル基としては、分岐であっても直鎖であってもよい、ヘキシル基、オクチル基、デシル基、ドデシル基、１，１，３−トリメチルブチル基、オレイル基、シクロヘキセニル基、アダマンチル基等を例として挙げることができる。
【００９６】
Ｒ_６及びＲ_７で表されるアルキル基、アルケニル基、アルキニル基、アリール基及び複素環基の代表例としては、一般式（ＩＩＩ）におけるＲ_１と同様の基を挙げることができる。Ｒ_６は、好ましくは水素原子、アルキル基であり、より好ましくは水素原子である。Ｒ_７は、好ましくはアルキル基、アリール基である。
【００９７】
Ｊ_１は好ましくは−ＮＲ_１１−である。Ｒ_１１は一般式（ＩＩＩ）におけるＲ_１と同義である。
【００９８】
前記一般式（Ｖ）において、Ｌは２価の連結基を表し、好ましくはアルキレン基、アリーレン基である。
【００９９】
前記一般式（Ｖ）において、ｎは０または１を表し、好ましくは０である。
前記一般式（ＶＩ）において、Ｒ_８、Ｒ_９及びＲ_１０が表すアルキル基、アルケニル基、アルキニル基、アリール基または複素環基としては、一般式（ＩＩＩ）におけるＲ_１と同様の基を挙げることができる。
【０１００】
前記一般式（ＶＩ）において、Ｌは２価の連結基を表し、好ましくはアルキレン基、アリーレン基である。
【０１０１】
前記一般式（ＶＩ）において、ｎは０または１を表し、好ましくは１である。
以下に、前記一般式（ＩＩＩ）〜一般式（ＶＩ）で表されるシアンカプラーの代表例を示すが、本発明はこれらに限定されるものではない。
【０１０２】
【化１７】

【０１０３】
【化１８】

【０１０４】
【化１９】

【０１０５】
【化２０】

【０１０６】
本発明に係る上記シアンカプラーは、通常ハロゲン化銀乳剤層において、ハロゲン化銀１モル当たり１×１０^−３〜１モル、好ましくは１×１０^−２〜８×１０^−１モルの範囲で用いることができる。
【０１０７】
本発明に係るシアンカプラーは、色相の観点から比誘電率が６以上の化合物と共に用いることが好ましい。
【０１０８】
本発明に係るマゼンタ色画像、シアン色画像及びイエロー色画像の分光吸収特性を調整するために、色調調整作用を有する化合物を添加することが好ましい。
【０１０９】
請求項２に係る発明の特徴の一つは、イエロー画像形成ユニットに前記一般式（Ｉ）で表されるカプラーと共にリン酸エステルまたはホスフィンオキサイド化合物を含有することにあり、好ましくは下記一般式（ＩＸ）で表される化合物を挙げることができる。
【０１１０】
【化２１】

【０１１１】
一般式（ＩＸ）において、Ｒ_２１、Ｒ_２２及びＲ_２３は各々脂肪族基または芳香族基を表し、ｐ、ｑ及びｒは各々０または１を表す。
【０１１２】
Ｒ_２１、Ｒ_２２及びＲ_２３で表される脂肪族基としては、炭素数１〜３０、好ましくは１〜２０の直鎖または分岐したアルキル、アルケニル、アルキニルまたはシクロアルキル基があげられる。具体的には、例えば、メチル、エチル、プロピル、ブチル、ヘキシル、デシル、ドデシル、イソプロピル、ｔ−ブチル、２−エチルヘキシル、アリル、２−ブテニル、７−オクテニル、プロパルギル、２−ブチニル、シクロプロピル、シクロペンチル、シクロヘキシル、シクロドデシル等の基があげられる。Ｒ_２１、Ｒ_２２及びＲ_２３で表される芳香族基としては、炭素数６〜２０のものがあげられ、具体的には、例えば、フェニル、ナフチル、アントラニル等の各基があげられる。これらＲ_２１、Ｒ_２２及びＲ_２３で表される脂肪族基、芳香族基は更に置換されていてもよく、置換基としては、特に制限はないが、代表的にはアルキル、アリール、アニリノ、アシルアミノ、スルホンアミド、アルキルチオ、アリールチオ、アルケニル、シクロアルキル等の各基が挙げられるが、この他にハロゲン原子及びシクロアルケニル、アルキニル、複素環、スルホニル、スルフィニル、ホスホニル、アシル、カルバモイル、スルファモイル、シアノ、アルコキシ、アリールオキシ、複素環オキシ、シロキシ、アシルオキシ、スルホニルオキシ、カルバモイルオキシ、アルキルアミノ、イミド、ウレイド、スルファモイルアミノ、アルコキシカルボニルアミノ、アリールオキシカルボニルアミノ、アルコキシカルボニル、複素環チオ、チオウレイド、カルボキシル、ヒドロキシル、メルカプト、ニトロ、スルホ等の各基、並びにスピロ化合物残基、有橋炭化水素化合物残基等も挙げられる。
【０１１３】
以下に、前記一般式（ＩＸ）で表される化合物の代表的具体例を示すが、本発明はこれらに限定されるものではない。
【０１１４】
【化２２】

【０１１５】
請求項２に係る発明の特徴の一つは、マゼンタ画像形成ユニットに前記一般式（ＩＩ）で表される化合物と炭素原子数１０以上のアルコール化合物とリン酸エステルまたはホスフィンオキサイド化合物とを含有することにある。炭素原子数１０以上のアルコール化合物としては、好ましくは下記一般式（Ｘ）で表される化合物を挙げることができる。
【０１１６】
【化２３】

【０１１７】
一般式（Ｘ）において、Ｒ_３１は、ａ）非置換アルキル基または非置換アルケニル基、ｂ）置換されたアルキル基または置換されたアルケニル基（ただし、該置換された各基は、アリール基、アルケニル基、ハロゲン原子、アルコキシカルボニル基及びアシルオキシ基から選ばれる少なくとも１つの置換基を含む）、ｃ）非置換アリール基、及びｄ）アルキル基、アルコキシ基、アルコキシカルボニル基及びアシルオキシ基から選ばれる少なくとも１つの置換基を含むアリール基、からなる群から選択され、Ｒ_３２及びＲ_３３は、各々独立に水素原子またはＲ_３１で表される群の基から選択されるが、Ｒ_３１、Ｒ_３２及びＲ_３３に含まれる炭素原子の総数は１０以上であり、好ましくは１０〜３０である。
【０１１８】
前記一般式（Ｘ）において、好ましくは、Ｒ_３１が置換若しくは非置換のアルキル基、または置換若しくは非置換のアルケニル基である。さらに好ましくは、Ｒ_３２及びＲ_３３の少なくとも１つが水素原子であるか、またはＲ_３２及びＲ_３３の少なくとも１つが、置換若しくは非置換のアルキル基、または置換若しくは非置換のアルケニル基である。例えば、Ｒ_３１が直鎖または分岐のアルキル基であり、Ｒ_３２及びＲ_３３が水素原子をとる場合には、一般式（Ｘ）はＣ_ｍＨ_２ｍ−１−ＯＨ（ただし、ｍは好ましくは１０〜約３０の整数である）で表される。また、Ｒ_３１及びＲ_３２が独立に直鎖または分岐アルキルであり、Ｒ_３３が水素原子をとる場合には、一般式（Ｘ）はＣ_ｎＨ_２ｎ−１ＣＨ（Ｃ_ｍＨ_２ｍ−１）ＯＨ（ただし、ｎ＋ｍは好ましくは、９〜約２９の範囲である）で表される。また、Ｒ_３１が直鎖または分岐のアルケニル基であり、Ｒ_３２及びＲ_３３が水素原子をとる場合には、一般式（Ｘ）は（Ｃ_ｍＨ_２ｍ−１）ＣＨ＝ＣＨ（ＣＨ_２）_ｎＣＨ_２−ＯＨ（ただし、ｍ＋ｎは好ましくは７〜約２７の整数である）で表される。また、Ｒ_３１がアリール置換のアルキル基であり、Ｒ_３２及びＲ_３３が水素原子をとる場合には、一般式（Ｘ）は（Ｃ_２Ｈ_４）Ｃ_ｎＨ_２ｎ−ＯＨ（ただし、ｎは好ましくは４〜約２４の整数である）で表される。特に好ましくは、Ｒ_３１が置換または非置換のアリール基であり、Ｒ_３２及びＲ_３３の少なくとも１つが水素原子をとる場合である。
【０１１９】
以下に、前記一般式（Ｘ）で表される炭素原子数１０以上のアルコール化合物の代表的具体例を示すが、本発明はこれらに限定されるものではない。
【０１２０】
【化２４】

【０１２１】
また、炭素原子数１０以上のアルコール化合物と併用して用いられるリン酸エステルまたはホスフィンオキサイド化合物の好ましい化合物として、前記一般式（ＩＸ）で表される化合物を挙げることができる。
【０１２２】
前記炭素原子数１０以上のアルコール化合物及びリン酸エステルまたはホスフィンオキサイド化合物の総量とマゼンタカプラーとの添加量比は、０．１：１〜１０：１の質量比の範囲で使用することができ、また、炭素原子数１０以上のアルコール化合物及びリン酸エステルまたはホスフィンオキサイド化合物との比は、１：９９〜９９：１の任意の混合比を選択することができる。
【０１２３】
請求項２に係る発明の特徴の一つは、シアン画像形成ユニット中に前記一般式（ＩＩＩ）で表される化合物を少なくとも１種と比誘電率が６以上の高沸点有機溶媒を含有することにある。カプラーの構造との関わりに起因すると思われるが、比誘電率の小さい化合物を用いた場合には、シアン画像に適した色相の色素が得られ難いという欠点がある。ここにいう高沸点有機溶媒とは、常圧での沸点がおよそ１７５℃以上であり、感光材料中に残留し、種々の機能を発揮するものをいい、単独の化合物であってもよいし、混合物であってもよい。混合物の場合には、混合物としての比誘電率が６以上であることが必要である。比誘電率が高いことからも予想されるように、極性構造（カルボン酸エステル、カルボン酸アミド、リン酸エステル、リン酸アミド、ホスホン酸エステル、ホスホン酸アミド、ホスフィン酸エステル、ホスフィン酸アミド、ホスホリル、炭素原子に結合するヒドロキシル基、炭素原子に結合するハロゲン原子、両端で炭素原子に結合する酸素原子、または３つの炭素原子に結合する窒素原子）を有することが好ましい。
【０１２４】
本発明に用いられる高沸点有機溶媒は、常温・常圧で液体であっても固体であってもよく、あるいは低分子量化合物であっても高分子量（またはポリマー状）の化合物であってもよい。
【０１２５】
本発明において、高沸点有機溶媒の定義として、以下に列挙されるような特性を主たる機能として有することが当業者において既知である化合物は除く。例えば、褪色防止剤（ラジカルスカベンジャー、エネルギー消光剤など）、紫外線吸収剤、現像主薬酸化体スカベンジャー（混色防止剤、硬調化剤、競争化合物）、現像主薬スカベンジャー、処理後画像の増色防止剤、光・熱・湿度によるステイン防止剤、ブリーチステイン防止剤などは高沸点有機溶媒の範疇には含まない。
【０１２６】
本発明でいう比誘電率とは、真空に対する比誘電率であり、変性器ブリッジ法等の方法により、容易に測定することができる。本発明においては、測定温度２５℃、測定周波数１０ｋＨｚで測定した値を用いた。高沸点有機溶媒を混合して使用する場合は、高沸点有機溶媒の混合物の比誘電率を測定する。高沸点有機溶媒が常温で固体の場合には、比誘電率は加熱融解し過冷却液体として測定するか、比誘電率が既知の高沸点有機溶媒との混合比率を変化させて混合して比誘電率を測定し、質量分率対比誘電率のプロットの外挿値として求めることができる。
【０１２７】
具体的な化合物と測定値は、特開２００１−１１７２０５号などに詳しく記載されている。
【０１２８】
以下に、比誘電率が６以上の高沸点有機溶媒の例を挙げるが、本発明はこれに限定されるものではない。
【０１２９】
【化２５】

【０１３０】
本発明に係る感光材料において、ハロゲン化銀乳剤層は支持体上に積層塗布されるが支持体からの順番はどのような順番でもよい。この他に必要に応じ中間層、フィルター層、保護層等を配置することができる。
【０１３１】
前記マゼンタ、シアン、イエローの各カプラーには、形成された色素画像の光、熱、湿度等による褪色を防止するため褪色防止剤を併用することができる。好ましい化合物としては、特開平２−６６５４１号３ページ記載の一般式Ｉ及びＩＩで示されるフェニルエーテル系化合物、特開平３−１７４１５０号記載の一般式ＩＩＩＢで示されるフェノール系化合物、特開平６４−９０４４５号記載の一般式Ａで示されるアミン系化合物、特開昭６２−１８２７４１号記載の一般式ＸＩＩ、ＸＩＩＩ、ＸＩＶ、ＸＶで示される金属錯体が、特にマゼンタ色素用として好ましい。また、特開平１−１９６０４９号記載の一般式Ｉ′で示される化合物及び特開平５−１１４１７号記載の一般式ＩＩで示される化合物が特にイエロー、シアン色素用として好ましい。
【０１３２】
本発明に係るハロゲン化銀感光材料に用いられるステイン防止剤やその他の有機化合物を添加するのに水中油滴型乳化分散法を用いる場合には、通常、沸点１５０℃以上の水不溶性高沸点有機溶媒に、必要に応じて低沸点及び／または水溶性有機溶媒を併用して溶解し、ゼラチン水溶液などの親水性バインダー中に界面活性剤を用いて乳化分散する。分散手段としては、撹拌機、ホモジナイザー、コロイドミル、フロージェットミキサー、超音波分散機等を用いることができる。分散後、または、分散と同時に低沸点有機溶媒を除去する工程を入れてもよい。ステイン防止剤等を溶解して分散するために用いることのできる高沸点有機溶媒としては、トリクレジルホスフェート、トリオクチルホスフェート等のリン酸エステル類、トリオクチルホスフィンオキサイド等のホスフィンオキサイド類、特開平４−２６５９７５号の５ページに記載の（ａ−ｉ）〜（ａ−ｘ）を代表とする高級アルコール系化合物等が好ましく用いられる。また高沸点有機溶媒の誘電率としては３．５〜７．０であることが好ましい。また二種以上の高沸点有機溶媒を併用することもできる。
【０１３３】
本発明に係る感光材料に用いられる写真用添加剤の分散や塗布時の表面張力調整のため用いられる界面活性剤として好ましい化合物としては、１分子中に炭素数８〜３０の疎水性基とスルホン酸基またはその塩を含有するものが挙げられる。具体的には、特開昭６４−２６８５４号に記載のＡ−１〜Ａ−１１が挙げられる。また、アルキル基に弗素原子を置換した界面活性剤も好ましく用いられる。これらの分散液は通常ハロゲン化銀乳剤を含有する塗布液に添加されるが、分散した後塗布液に添加されるまでの時間及び塗布液に添加した後塗布するまでの時間は短いほうがよく、各々１０時間以内が好ましく、３時間以内がより好ましく、２０分以内が特に好ましい。
【０１３４】
本発明に係るハロゲン化銀感光材料には、現像主薬酸化体と反応する化合物を感光性層と感光性層の間の層に添加して色濁りを防止したり、またハロゲン化銀乳剤層に添加してカブリ等を改良することが好ましい。このための化合物としてはハイドロキノン誘導体が好ましく、さらに好ましくは２，５−ジ−ｔ−オクチルハイドロキノンのようなジアルキルハイドロキノンである。特に好ましい化合物は特開平４−１３３０５６号記載の一般式ＩＩで示される化合物であり、同号１３〜１４ページ記載の化合物ＩＩ−１〜ＩＩ−１４及び１７ページ記載の化合物１が挙げられる。
【０１３５】
本発明に係る感光材料中には、紫外線吸収剤を添加してスタチックカブリを防止したり色素画像の耐光性を改良することが好ましい。好ましい紫外線吸収剤としてはベンゾトリアゾール類が挙げられ、特に好ましい化合物としては特開平１−２５０９４４号記載の一般式ＩＩＩ−３で示される化合物、特開昭６４−６６６４６号記載の一般式ＩＩＩで示される化合物、特開昭６３−１８７２４０号記載のＵＶ−１Ｌ〜ＵＶ−２７Ｌ、特開平４−１６３３号記載の一般式Ｉで示される化合物、特開平５−１６５１４４号記載の一般式（Ｉ）、（ＩＩ）で示される化合物が挙げられる。
【０１３６】
本発明に係る感光材料には、油溶性染料や顔料を含有すると白地性が改良され好ましい。油溶性染料の代表的具体例は、特開平２−８４２号８〜９ページに記載の化合物１〜２７があげられる。
【０１３７】
本発明に係るハロゲン化銀感光材料には、バインダーとしてゼラチンを用いることが有利であるが、必要に応じて他のゼラチン、例えば、ゼラチン誘導体、ゼラチンと他の高分子のグラフトポリマー、ゼラチン以外のタンパク質、糖誘導体、セルロース誘導体、単一あるいは共重合体のごとき合成親水性高分子物質等の親水性コロイドも用いることができる。
【０１３８】
これらバインダーの硬膜剤としては、ビニルスルホン型硬膜剤やクロロトリアジン型硬膜剤を単独または併用して使用することが好ましい。特開昭６１−２４９０５４号、同６１−２４５１５３号記載の化合物を使用することが好ましい。また、写真性能や画像保存性に悪影響するカビや細菌の繁殖を防ぐためコロイド層中に特開平３−１５７６４６号記載のような防腐剤及び抗カビ剤を添加することが好ましい。また、感光材料または処理後の感光材料表面の物性を改良するため、保護層に特開平６−１１８５４３号や特開平２−７３２５０号記載の滑り剤やマット剤を添加することが好ましい。
【０１３９】
本発明に係る感光材料に用いる支持体としては、どのような材質を用いてもよく、ポリエチレンやポリエチレンテレフタレートで被覆した紙、天然パルプや合成パルプからなる紙支持体、塩化ビニルシート、白色顔料を含有してもよいポリプロピレン、ポリエチレンテレフタレート支持体、バライタ紙などを用いることができる。なかでも、原紙の両面に耐水性樹脂被覆層を有する支持体が好ましい。耐水性樹脂としてはポリエチレンやポリエチレンテレフタレートまたはそれらのコポリマーが好ましい。
【０１４０】
紙の表面に耐水性樹脂被覆層を有する支持体は、通常、５０〜３００ｇ／ｍ^２の質量を有する表面の平滑なものが用いられるが、プルーフ画像を得る目的に対しては、取り扱いの感覚を印刷用紙に近づけるため、１３０ｇ／ｍ^２以下の原紙が好ましく用いられ、さらに７０〜１２０ｇ／ｍ^２の原紙が好ましく用いられる。本発明に用いられる支持体としては、ランダムな凹凸を有するものであっても平滑なものであっても好ましく用いることができる。
【０１４１】
支持体に用いられる白色顔料としては、無機及び／または有機の白色顔料を用いることができ、好ましくは無機の白色顔料が用いられる。例えば、硫酸バリウム等のアルカリ土類金属の硫酸塩、炭酸カルシウム等のアルカリ土類金属の炭酸塩、微粉ケイ酸、合成ケイ酸塩等のシリカ類、ケイ酸カルシウム、アルミナ、アルミナ水和物、酸化チタン、酸化亜鉛、タルク、クレイ等があげられる。白色顔料は好ましくは硫酸バリウム、酸化チタンである。支持体表面の耐水性樹脂層中に含有される白色顔料の量は、鮮鋭性を改良するうえで１３質量％以上が好ましく、さらには１５質量％が好ましい。
【０１４２】
本発明に係る紙支持体の耐水性樹脂層中の白色顔料の分散度は、特開平２−２８６４０号に記載の方法で測定することができる。この方法で測定したときに、白色顔料の分散度が前記公報に記載の変動係数として０．２０以下であることが好ましく、０．１５以下であることがより好ましい。
【０１４３】
本発明に用いられる両面に耐水性樹脂層を有する紙支持体の樹脂層は、１層であってもよいし、複数層からなってもよい。複数層とし、乳剤層と接する方に白色顔料を高濃度で含有させると鮮鋭性の向上が大きく、プルーフ用画像を形成するのに好ましい。
【０１４４】
また、支持体表面の中心面平均粗さ（ＳＲａ）の値が０．１５μｍ以下、さらには０．１２μｍ以下であるほうが写真用途にとって光沢性がよいという効果が得られより好ましい。プルーフの用途においては、印刷物との近似性という観点から０．８〜２μｍのものが好ましく用いられる。
【０１４５】
本発明に係る感光材料では、必要に応じて支持体表面にコロナ放電、紫外線照射、火炎処理等を施した後、直接または下塗層（支持体表面の接着性、帯電防止性、寸度安定性、耐摩擦性、硬さ、ハレーション防止性、摩擦特性及び／またはその他の特性を向上するための１または２以上の下塗層）を介して塗布されていてもよい。
【０１４６】
ハロゲン化銀乳剤を用いた感光材料の塗布に際して、塗布性を向上させるために増粘剤を用いてもよい。塗布法としては２種以上の層を同時に塗布することのできるエクストルージョンコーティング及びカーテンコーティングが特に有用である。
【０１４７】
本発明に用いられる露光装置の露光光源は、公知のものをいずれも好ましく用いることができるが、レーザーまたは発光ダイオード（以下ＬＥＤと表す）がより好ましく用いられる。
【０１４８】
レーザーとしては、半導体レーザー（以下、ＬＤと表す）がコンパクトであること、光源の寿命が長いことから好ましく用いられる。また、ＬＤはＤＶＤ、音楽用ＣＤの光ピックアップ、ＰＯＳシステム用バーコードスキャナ等の用途や光通信等の用途に用いられており、安価であり、かつ比較的高出力のものが得られるという長所を有している。ＬＤの具体的な例としては、アルミニウム・ガリウム・インジウム・ヒ素（６５０ｎｍ）、インジウム・ガリウム・リン（〜７００ｎｍ）、ガリウム・ヒ素・リン（６１０〜９００ｎｍ）、ガリウム・アルミニウム・ヒ素（７６０〜８５０ｎｍ）等を挙げることができる。最近では、青光を発振するレーザーも開発されているが、現状では、６１０ｎｍよりも長波の光源としてＬＤを用いるのが有利である。
【０１４９】
ＳＨＧ素子を有するレーザー光源としては、ＬＤ、ＹＡＧレーザーから発振される光をＳＨＧ素子により半分の波長の光に変換して放出させるものであり、可視光が得られることから適当な光源がない緑〜青の領域の光源として用いられる。この種の光源の例としては、ＹＡＧレーザーにＳＨＧ素子を組み合わせたもの（５３２ｎｍ）等がある。
【０１５０】
ガスレーザーとしては、ヘリウム・カドミウムレーザー（約４４２ｎｍ）、アルゴンイオンレーザー（約５１４ｎｍ）、ヘリウムネオンレーザー（約５４４ｎｍ、６３３ｎｍ）等が挙げられる。
【０１５１】
ＬＥＤとしては、ＬＤと同様の組成をもつものが知られているが、青〜赤外まで種々のものが実用化されている。
【０１５２】
本発明に用いられる露光光源としては、各レーザーを単独で用いてもよいし、これらを組合せ、マルチビームとして用いてもよい。ＬＤの場合には、例えば１０個のＬＤを並べることにより１０本の光束からなるビームが得られる。一方、ヘリウムネオンレーザーのような場合、レーザーから発した光をビームセパレーターで例えば１０本の光束に分割する。
【０１５３】
露光用光源の強度変化は、ＬＤ、ＬＥＤのような場合には、個々の素子に流れる電流値を変化させる直接変調を行うことができる。ＬＤの場合には、ＡＯＭ（音響光学変調器）のような素子を用いて強度を変化させてもよい。ガスレーザーの場合には、ＡＯＭ、ＥＯＭ（電気光学変調器）等のデバイスを用いるのが一般である。
【０１５４】
光源にＬＥＤを用いる場合には、光量が弱ければ、複数の素子で同一の画素を重複して露光する方法を用いてもよい。
【０１５５】
また、これらに代わる光源として有機発光素子を用いてもよく、これらについては、例えば、特開２０００−２５８８４６等に記載されている。
【０１５６】
本発明の特徴の一つは、露光装置の解像度が１０００ｄｐｉ以上であることにあるが、これは、露光の最小ビーム径が２５．４μｍ以下であることを意味する。なお、本発明でいうｄｐｉとは、２．５４ｃｍ当たりのドット数を表す。
【０１５７】
露光装置の解像度が小さい所では、２次色、３次色の網点％の変化による連続現像処理（ランニング処理）前後での色相変動は小さくなるが、明瞭な面積変調画像の形成は困難となり、本発明に用いるのに適さない。また、６μｍより小さいと画質的には好ましいが、色調の調整が困難であったり、処理速度が低下したりする。
【０１５８】
本発明において面積変調あるいは面積変調画像という言葉を用いているが、これは画像上の濃淡を個々の画素の色の濃淡で表現するのではなく、特定の濃度に発色した部分の面積の大小で表現することを意味し、網点と同義と考えてよい。また、濃度変調、濃度変調画像という言葉を用いているが、これは画素の色の濃淡を濃度を変えて表現することを意味し、広い意味では連続階調画像と同義である。
【０１５９】
本発明の特徴の一つは、濃度を変更可能な画素（以下ドットともいう）の集合体として網点を形成することにある。デジタルデータに基づき面積階調画像を形成するシステムでは、網点をさらに小さな画素に分割し、この画素を適切な露光量で露光する事によってその集合体として網点を再現することが可能である。例えとして簡単な例を挙げれば、１つの網点が１００個の画素で構成されるのであれば、５０個の画素を現像可能なように露光する事により網％が５０％の網点を形成する事ができる。通常面積階調露光であればＹ、Ｍ、Ｃ、墨の発色をさせることで目的を達することができる。しかし、濃度を変更することができるとオーバープリントカラー、特色を再現することができプルーフ画像の有用性が著しく高いものとなる。
【０１６０】
本発明の特徴の一つは、ハロゲン化銀感光材料の露光量と画像色素の量に対応する量の関係と画素の色と画像色素の量に対応する量の関係を利用して画像形成に必要な露光量を求めることにある。画像色素の量に対応する量とは、画像色素の量と１対１で対応する量であれば何であっても好ましく用いることができる。極端な場合には色素の量そのものであっても構わない。画像色素の量に対応する量としては、印刷の分野でもよく用いられる濃度（光学濃度）やＣＩＥＬＡＢ色空間の座標などを用いることができる。例えば、Ｙ色素であればＢ濃度、ＣＩＥＬＡＢ色空間のｂ^＊等が適切である。また、これらは適宜組みあわせた量として用いられてもよく、例えばＣ色素であればＣＩＥＬＡＢ色空間でのメトリッククロマ等を用いることができる。これらの内で適切なものの一つとしてアナリティカル濃度を挙げることができる。
【０１６１】
アナリティカル濃度は写真の分野でよく用いられる濃度の概念であるが、Ｙ、Ｍ、Ｃ色素を任意の量で発色させた時、Ｙ色素だけを同量発色させたときのＢ濃度をアナリティカルＢ濃度と呼び、Ｍ色素だけを同量発色させたときのＧ濃度をアナリティカルＧ濃度、Ｃ色素だけを同量発色させたときのＲ濃度をアナリティカルＲ濃度と呼ぶ。アナリティカル濃度は概念的な量であるが、計算によって求めることもできる。アナリティカル濃度に関しては、Ｔ．Ｈ．Ｊａｍｅｓ編、Ｔｈｅ Ｔｈｅｏｒｙ ｏｆ Ｔｈｅ Ｐｈｏｔｏｇｒａｐｈｉｃ Ｐｒｏｃｅｓｓ、Ｍａｃｍｉｌｌａｎ、Ｎｅｗｙｏｒｋ、ｐ．５２４−５２９（１９７７）に記載されており、これを参考に求めることができる。本発明の有用な態様として反射支持体を有するハロゲン化銀感光材料を使用したシステムを挙げることができ、この場合は、アナリティカル濃度も反射濃度として表しておくことが好ましい。数値の取り扱いの点からは、本来のアナリティカル濃度から変換した数値であってもよく、アナリティカル濃度を１００倍して整数化した方が扱いやすく、好ましい。
【０１６２】
本発明において、ハロゲン化銀感光材料の露光量と画像色素の量に対応する量（ここではアナリティカル濃度）の関係と述べているが、図２の感光材料特性ＴＢＬはこの一例である。露光量と濃度の関係を、任意の刻みで露光量を変化した全ての組み合わせでカラーパッチを作成し、これを測定した結果をデータベースとしておけば任意の色を与えられた時、このデータベースを参照することにより各層の露光量を求めることができる。しかし、この場合、精度を上げるためには膨大な量の測定を行い、データベースを作成する必要がある。一方、アナリティカル濃度により表現する方式においては、Ｙ、Ｍ、Ｃ各層の露光量と発色濃度の関係を求めておくことで少ないデータで精度よく必要な露光量を求めることが可能となり、システムの設計段階あるいは感光材料の色材の変更などに対しての対応が容易であるというメリットを有する。２次色の再現色を容易に所望の色に再現できることは、その網点％変化した色の色相が安定して再現されることに相まって本発明のカラー画像形成方法の価値を高めるものである。ここにいうアナリティカル濃度は分光条件などを特に規定する必要はなく、所望の濃度を規定するデータと、前記画像形成材料の特性を記述する濃度が同じ定義であればよい。印刷の分野で一般に用いられるステータスＴを用いてもよいし、精度を高めるには、分光濃度分布と分光積の関係からステータスＡを用いることも好ましい。
【０１６３】
本発明において、画素の色と画像色素の量に対応する量（この場合は、アナリティカル濃度）の関係と述べているが、図２の色毎の感光層の濃度ＴＢＬはこの一例である。
【０１６４】
次に画像データを露光用のデータに編集していく処理作業について図１、図２により説明する。まずデータを読み込む画素の番号（カウンタ：ｉ）を１に設定し、画素１のＹ、Ｍ、Ｃ、Ｋ、特色画像データを読み込む。次にどの色が発色しているのかを組み合わせて画素の色を判断する。これはテーブルを参照することにより達成される。たとえば画素１ではＹのみが発色しているので画素の色の判別ＴＢＬのＹのみが１になっている欄で、画素の色はＹであると判断される。画素３ではＹとＭが発色しているため画素の色はＲとなる。同様に画素４はＫのみ発色しているため色もＫであり、画素５はＫとＭが発色しているので画素の色はオーバープリント色であるＫ＋Ｍとなる。こうした変換により画素別画像データを作成する。次に、この色を作り出すためにＹ、Ｍ、Ｃ各画像形成層に与えるべき露光量をテーブルから読みとり、各画素毎に各層に与える露光量を並べた画像データとし、このデータを画像出力手段へ転送する。
【０１６５】
この作業の具体的な流れを、ハロゲン化銀感光材料の特性をアナリティカル濃度（１００倍して整数化してある）で表した例で説明する。画素の色から色毎の各感光層の濃度ＴＢＬを参照して各層のアナリティカル濃度を求める。この例では、画素１はＹのみレベル１（アナリティカル濃度１１０）に発色させることがわかる。これを基に感光材料特性ＴＢＬからＹの露光量はレベル（ｎ−４）であることが分かる。同様にしてＭ、Ｃについて露光量レベルを決めることができる。画素毎の露光量データが作成される。
【０１６６】
画素毎の処理が終わるとカウンタを＋１して次の画素についての処理を行う。以下これを繰り返し各画素毎の露光量のデータを作成する。画像出力手段へのデータ転送のタイミングは画素単位で行ってもよいし、１回の主走査に必要なデータの処理が終わった時点でもよいし、全てのデータ処理が終了した時点であってもよい。画像出力手段ではこのデータを必要に応じてデバイスを制御する信号に変換して露光を行う。
【０１６７】
画像出力手段では、前記露光量データをもとに必要に応じて露光デバイスの駆動信号に変換し、露光を行う。この露光デバイスの駆動信号に変換するプロセスは、画像処理手段の中に含ませることもできる。画像出力手段では、必要に応じてデータバッファを設け、露光のタイミングを調整してもよい。
【０１６８】
この時に想定したデータの構造を図２に示した。画像データとしては、画素の順に各色が発色しているかどうかのデータのみを持つものと想定した。Ｙ、Ｍ、Ｃ、Ｋ、特色の発色の有無の組み合わせのパターンから、テーブルを参照して画素の色が判断される。次に画素の色とＹ、Ｍ、Ｃ画像形成形成層の露光量のテーブルを参照し各層に与えるべき露光量が決定される。画素の色を判断する所と画素の色から各画像形成層の露光量を決定する所を分離しているのは、例えばＲを単色のＹとＭの単なる足し算ではなく独立に設定できるようにしたもので、要求する仕様により単純な足し算で表現してもよい。このように独立して設定できるようにすることで、より印刷に近似な画像を得ることができるし、また２つの画像データを使って緑と赤の２色で印刷するような場合の画像のチェックにも用いることができ、有用性の高いシステムが実現できる。
【０１６９】
上記の説明は、露光デバイスが一つのケースについて述べているが、露光デバイスが副走査方向に１０個並べられている場合であれば、画素１〜１０が副走査方向に並んだ画素を表し、主走査方向に１画素分ずれたデータは画素１１〜２０で表すというように読み替えて考えればよい。
【０１７０】
一般に濃度が低いところでは僅かの濃度の変動でも色の変化としてめだちやすくなるという傾向がある。網点の濃度を変化させられるというシステムは、前記のように種々の長所を有しているが、逆に変動が目立ちやすい領域を使用する可能性があり、より色を安定化させることが望まれている。ハロゲン化銀感光材料の保存状態によらず２次色の網点％の変化による連続現像処理前後での色相変動が小さいという本願発明の効果は、網点濃度を変化させられるシステムが求める色の安定度を高める手段として有用である。
【０１７１】
請求項３に記載の発明の特徴の一つは、原画像に特定のパターンを重ねた画像を濃度変調画像として出力することにあり、例えば、グリッド状に画素を区切るパターンを原画像に上書きした画像を、画素毎に均一な濃度として濃度変調画像として出力することにより網点％違いに相当する画像を色相の変動を小さく描写することが可能となる。
【０１７２】
このような光で画像を描くには、ハロゲン化銀感光材料上を光束が走査する必要があるが、感光材料を円筒状のドラムに巻き付けこれを高速に回転しながら回転方向に直角な方向に光束を動かす円筒外面走査方式をとってもよく、円筒状の窪みにハロゲン化銀感光材料を密着させて露光する円筒内面走査方式も好ましく用いることができる。多面体ミラーを高速で回転させこれによって搬送されるハロゲン化銀感光材料を搬送方向に対して直角に光束を移動して露光する平面走査方式をとってもよい。高画質であり、かつ大きな画像を得るには円筒外面走査方式がより好ましく用いられる。
【０１７３】
円筒外面走査方式での露光を行うには、ハロゲン化銀感光材料は正確に円筒状のドラムに密着されなければならない。これが的確に行われるためには、正確に位置合わせされて搬送される必要がある。本発明に用いられるハロゲン化銀感光材料は露光する側の面が外側に巻かれたものがより的確に位置合わせでき、好ましく用いることができる。同様な観点から、本発明に用いられるハロゲン化銀感光材料に用いられる支持体は適正な剛度があり、テーバー剛度で０．８〜４．０が好ましい。
【０１７４】
ドラム径は、露光するハロゲン化銀感光材料の大きさに適合させて任意に設定することができる。ドラムの回転数も任意に設定できるがレーザー光のビーム径、エネルギー強度、書き込みパターンや感光材料の感度などにより適当な回転数を選択することができる。生産性の観点からは、より高速な回転で走査露光できる方が好ましいが、具体的には１分間に２００〜３０００回転が好ましく用いられる。
【０１７５】
ドラムへのハロゲン化銀感光材料の固定方法は、機械的な手段によって固定させてもよいし、ドラム表面に吸引できる微小な穴を感光材料の大きさに応じて多数設けておき、感光材料を吸引して密着させることもできる。感光材料をドラムにできるだけ密着させることが画像ムラ等のトラブルを防ぐには重要である。
【０１７６】
請求項５に係る発明の特徴の１つは、露光装置が、デジタル画像情報とデバイスに依存しない画像データとを対応づける印刷条件プロファイル、及び前記デバイスに依存しない画像データと露光用デジタル画像データとを対応づける露光条件プロファイルとに基づいて、前記デジタル画像情報を前記露光用デジタル画像データに変換する色変換手段を有することにある。これはいわゆるカラーマネージメントシステム（ＣＭＳ）として知られるが、色域を最大限に使用するために、ＣＭＳの中で、ベタ部には他の色が混色しないように制限する等の制約が行われたりしているが、ベタ部に他の色素を特定の濃度以下の領域で濃度変調して発色させ色調調整を行ってもよい。
【０１７７】
本発明において用いられる芳香族一級アミン現像主薬としては、公知の化合物を用いることができる。これらの化合物の例として下記の化合物を挙げることができる。
【０１７８】
ＣＤ−１：Ｎ，Ｎ−ジエチルーｐ−フェニレンジアミン
ＣＤ−２：２−アミノ−５−ジエチルアミノトルエン
ＣＤ−３：２−アミノー５−（Ｎ−エチル−Ｎ−ラウリルアミノ）トルエン
ＣＤ−４：４−（Ｎ−エチル−Ｎ−（β−ヒドロキシエチル）アミノ）アニリン
ＣＤ−５：２−メチル−４−（Ｎ−エチル−Ｎ−（β−ヒドロキシエチル）アミノ）アニリン
ＣＤ−６：４−アミノ−３−メチル−Ｎ−エチル−Ｎ−（β−（メタンスルホンアミド）エチル）−アニリン
ＣＤ−７：Ｎ−（２−アミノ−５−ジエチルアミノフェニルエチル）メタンスルホンアミド
ＣＤ−８：Ｎ，Ｎ−ジメチル−ｐ−フェニレンジアミン
ＣＤ−９：４−アミノ−３−メチル−Ｎ−エチル−Ｎ−メトキシエチルアニリン
ＣＤ−１０：４−アミノ−３−メチル−Ｎ−エチル−Ｎ−（β−エトキシエチル）アニリン
ＣＤ−１１：４−アミノ−３−メチル−Ｎ−エチル−Ｎ−（γ−ヒドロキシプロピル）アニリン
請求項６に係る発明においては、発色現像主薬として、例示化合物ＣＤ−６である４−アミノ−３−メチル−Ｎ−エチル−Ｎ−（β−（メタンスルホンアミド）エチル）アニリンを用いることが好ましい。この現像主薬を用いることによりより安定した色相再現が可能となる。
【０１７９】
本発明においては、上記は発色現像主薬を含む発色現像液を任意のｐＨ域で使用できるが、迅速処理の観点からｐＨ９．５〜１３．０であることが好ましく、より好ましくはｐＨ９．８〜１２．０の範囲で用いられる。
【０１８０】
本発明に係る発色現像液の処理温度は、３５℃以上、７０℃以下が好ましい。温度が高いほど短時間の処理が可能であり好ましいが、処理液の安定性からはあまり高くない方が好ましく、３７℃以上６０℃以下で処理することが好ましい。
【０１８１】
発色現像時間は、従来一般には３分３０秒程度で行われているが、本発明では４０秒以内が好ましく、さらに２５秒以内の範囲で行うことがさらに好ましい。
【０１８２】
発色現像液には、前記の発色現像主薬に加えて、既知の現像液成分化合物を添加することができ、例えば、ｐＨ緩衝作用を有するアルカリ剤、塩化物イオン、ベンゾトリアゾール類等の現像抑制剤、保恒剤、キレート剤などが用いられる。
【０１８３】
本発明に係るハロゲン化銀感光材料は、発色現像後、漂白処理及び定着処理を施される。漂白処理は定着処理と同時に行なってもよい。定着処理の後は、通常は水洗処理が行なわれる。また、水洗処理の代替として、安定化処理を行なってもよい。本発明に係るハロゲン化銀感光材料の現像処理に用いる現像処理装置としては、処理槽に配置されたローラーに感光材料をはさんで搬送するローラートランスポートタイプであっても、ベルトに感光材料を固定して搬送するエンドレスベルト方式であってもよいが、処理槽をスリット状に形成して、この処理槽に処理液を供給するとともに感光材料を搬送する方式や処理液を噴霧状にするスプレー方式、処理液を含浸させた担体との接触によるウエッブ方式、粘性処理液による方式なども用いることができる。大量に処理する場合には、自動現像機を用いてランニング処理されるのが、この際、各処理液の補充液量は少ない程好ましく、環境適性等より最も好ましい処理形態は、補充方法として錠剤の形態で処理剤を添加することであり、公開技報９４−１６９３５に記載の方法が最も好ましい。
【０１８４】
【実施例】
以下、実施例により本発明を詳細に説明するが、本発明の態様はこれに限定されない。
【０１８５】
実施例１
片面に高密度ポリエチレンを、もう一方の面にアナターゼ型酸化チタンを１５質量％の含有量で分散して含む溶融ポリエチレンをラミネートした、１平米当たりの質量が１１５ｇのポリエチレンラミネート紙反射支持体（テーバー剛度＝３．５、ＰＹ値＝２．７μｍ）上に、表１の構成からなる各層を、酸化チタンを含有するポリエチレン層側に塗設し、更に、裏面側にはゼラチン６．００ｇ／ｍ^２、シリカマット剤０．６５ｇ／ｍ^２を塗設した多層ハロゲン化銀感光材料試料１０１を作製した。
【０１８６】
なお、表１に記載の各カプラーは、高沸点溶媒及び酢酸エチルに溶解し、界面活性剤を含むゼラチン溶液中に超音波分散機を用いて乳化・分散し、分散物として添加した。なお、界面活性剤として（ＳＵ−１）を用いた。又、硬膜剤として（Ｈ−１）、（Ｈ−２）を添加した。塗布助剤としては、界面活性剤（ＳＵ−２）、（ＳＵ−３）を添加し、表面張力を調整した。また各層には（Ｆ−１）を全量が０．０４ｇ／ｍ^２となるように添加した。
【０１８７】
【表１】

【０１８８】
ＳＵ−１：トリ−ｉ−プロピルナフタレンスルホン酸ナトリウム
ＳＵ−２：スルホ琥珀酸ジ（２−エチルヘキシル）・ナトリウム塩
ＳＵ−３：スルホ琥珀酸ジ（２，２，３，３，４，４，５，５−オクタフルオロペンチル）・ナトリウム塩
Ｈ−１：テトラキス（ビニルスルホニルメチル）メタン
Ｈ−２：２，４−ジクロロ−６−ヒドロキシ−ｓ−トリアジン・ナトリウム
ＨＱ−１：２，５−ジ−ｔ−オクチルハイドロキノン
ＨＱ−２：２，５−ジ（（１，１−ジメチル−４−ヘキシルオキシカルボニル）ブチル）ハイドロキノン
ＨＱ−３：２，５−ジ−ｓｅｃ−ドデシルハイドロキノンと２，５−ジ−ｓｅｃテトラデシルハイドロキノンと２−ｓｅｃ−ドデシル−５−ｓｅｃ−テトラデシルハイドロキノンの質量比１：１：２の混合物
ＳＯ−１：トリオクチルホスフィンオキサイド
ＳＯ−２：ジ（ｉ−デシル）フタレート
ＳＯ−３：オレイルアルコール
ＳＯ−４：トリクレジルホスフェート
ＰＶＰ：ポリビニルピロリドン
【０１８９】
【化２６】

【０１９０】
【化２７】

【０１９１】
上記試料１０１の作製に用いた各ハロゲン化銀乳剤の調製方法を以下に示す。〔青感光性ハロゲン化銀乳剤の調製〕
４０℃に保温した２％ゼラチン水溶液１リットル中に、下記（Ａ液）及び（Ｂ液）をｐＡｇ＝７．３、ｐＨ＝３．０に制御しつつ同時添加し、更に下記（Ｃ液）及び（Ｄ液）をｐＡｇ＝８．０、ｐＨ＝５．５に制御しつつ同時添加した。この時、ｐＡｇの制御は特開昭５９−４５４３７号記載の方法により行い、ｐＨの制御は硫酸又は水酸化ナトリウム水溶液を用いて適宜行った。
【０１９２】
（Ａ液）
塩化ナトリウム ３．４２ｇ
臭化カリウム ０．０３ｇ
水を加えて ２００ｍｌ
（Ｂ液）
硝酸銀 １０ｇ
水を加えて ２００ｍｌ
（Ｃ液）
塩化ナトリウム １０２．７ｇ
ヘキサクロロイリジウム（ＩＶ）酸カリウム ４×１０^−８モル
ヘキサシアノ鉄（ＩＩ）酸カリウム ２×１０^−５モル
臭化カリウム １．０ｇ
水を加えて ６００ｍｌ
（Ｄ液）
硝酸銀 ３００ｇ
水を加えて ６００ｍｌ
添加終了後、花王アトラス社製デモールＮの５％水溶液と硫酸マグネシウムの２０％水溶液を用いて脱塩を行った後、ゼラチン水溶液と混合して平均粒径０．７１μｍ、粒径分布の変動係数０．０７、塩化銀含有率９９．５モル％の単分散立方体乳剤であるＥＭＰ−１０１を得た。
【０１９３】
上記ＥＭＰ−１０１に対し、下記化合物を用いて６０℃で最適に化学増感を行い、青感光性ハロゲン化銀乳剤であるＥｍ−Ｂ１０１を得た。
【０１９４】
チオ硫酸ナトリウム ０．８ｍｇ／モルＡｇＸ
塩化金酸 ０．５ｍｇ／モルＡｇＸ
安定剤：ＳＴＡＢ−１ ３×１０^−４モル／モルＡｇＸ
安定剤：ＳＴＡＢ−２ ３×１０^−４モル／モルＡｇＸ
安定剤：ＳＴＡＢ−３ ３×１０^−４モル／モルＡｇＸ
増感色素：ＢＳ−１ ４×１０^−４モル／モルＡｇＸ
増感色素：ＢＳ−２ １×１０^−４モル／モルＡｇＸ
臭化カリウム ０．２ｇ／モルＡｇＸ
ＳＴＡＢ−１：１−フェニル−５−メルカプトテトラゾール
ＳＴＡＢ−２：１−（４−エトキシフェニル）−５−メルカプトテトラゾール
ＳＴＡＢ−３：１−（３−アセトアミドフェニル）−５−メルカプトテトラゾール
次いで、上記ＥＭＰ−１０１の調製において、（Ａ液）と（Ｂ液）の添加時間及び（Ｃ液）と（Ｄ液）の添加時間を変更した以外は同様にして、平均粒径０．６４μｍ、粒径分布の変動係数０．０７、塩化銀含有率９９．５モル％の単分散立方体乳剤であるＥＭＰ−１０２を得た。
【０１９５】
Ｅｍ−Ｂ１０１の調製において、ＥＭＰ−１０１に代えてＥＭＰ−１０２を用いた以外同様にしてＥｍ−Ｂ１０２を調製し、Ｅｍ−Ｂ１０１とＥｍ−Ｂ１０２の１：１の混合物を青感光性ハロゲン化銀乳剤として使用した。
【０１９６】
【化２８】

【０１９７】
（緑感光性ハロゲン化銀乳剤の調製）
上記ＥＭＰ−１０１の調製において、（Ａ液）と（Ｂ液）及び（Ｃ液）と（Ｄ液）の各添加時間を変更した以外は同様にして、平均粒径０．４０μｍ、変動係数０．０８、塩化銀含有率９９．５％の単分散立方体乳剤であるＥＭＰ−１０３を調製した。
【０１９８】
上記ＥＭＰ−１０３に対し、下記化合物を用い５５℃にて最適に化学増感を行い、緑感光性ハロゲン化銀乳剤であるＥｍ−Ｇ１０１を得た。
【０１９９】
チオ硫酸ナトリウム １．５ｍｇ／モルＡｇＸ
塩化金酸 １．０ｍｇ／モルＡｇＸ
安定剤：ＳＴＡＢ−１ ３×１０^−４モル／モルＡｇＸ
安定剤：ＳＴＡＢ−２ ３×１０^−４モル／モルＡｇＸ
安定剤：ＳＴＡＢ−３ ３×１０^−４モル／モルＡｇＸ
増感色素：ＧＳ−１ ２×１０^−４モル／モルＡｇＸ
増感色素：ＧＳ−２ ２×１０^−４モル／モルＡｇＸ
塩化ナトリウム ０．５ｇ／モルＡｇＸ
次いで、上記ＥＭＰ−１０３の調製において、（Ａ液）と（Ｂ液）の添加時間及び（Ｃ液）と（Ｄ液）の各添加時間を変更した以外は同様にして、平均粒径０．５０μｍ、変動係数０．０８、塩化銀含有率９９．５％の単分散立方体乳剤であるＥＭＰ−１０４を得た。
【０２００】
上記Ｅｍ−Ｇ１０１の調製において、ＥＭＰ−１０３に代えてＥＭＰ−１０４を用いた以外同様にしてＥｍ−Ｇ１０２を調製し、Ｅｍ−Ｇ１０１とＥｍ−Ｇ１０２の１：１の混合物を緑感光性ハロゲン化銀乳剤として使用した。
【０２０１】
【化２９】

【０２０２】
（赤感光性ハロゲン化銀乳剤の調製）
前記調製したＥＭＰ−１０３に対し、下記化合物を用い６０℃にて最適に化学増感を行い、赤感光性ハロゲン化銀乳剤であるＥｍ−Ｒ１０１を得た。
【０２０３】
チオ硫酸ナトリウム １．８ｍｇ／モルＡｇＸ
塩化金酸 ２．０ｍｇ／モルＡｇＸ
安定剤：ＳＴＡＢ−１ ２×１０^−４モル／モルＡｇＸ
安定剤：ＳＴＡＢ−２ ２×１０^−４モル／モルＡｇＸ
安定剤：ＳＴＡＢ−３ ２×１０^−４モル／モルＡｇＸ
安定剤：ＳＴＡＢ−４ １×１０^−４モル／モルＡｇＸ
増感色素：ＲＳ−１ １×１０^−４モル／モルＡｇＸ
増感色素：ＲＳ−２ １×１０^−４モル／モルＡｇＸ
強色増感剤：ＳＳ−１ ２×１０^−４モル／モルＡｇＸ
ＳＴＡＢ−４：ｐ−トルエンチオスルホン酸
次に、前記調製したＥＭＰ−１０３に対し、下記化合物を用いて６０℃にて最適に化学増感を行い、赤感光性ハロゲン化銀乳剤であるＥｍ−Ｒ１０２を得た。
【０２０４】
チオ硫酸ナトリウム １．８ｍｇ／モルＡｇＸ
塩化金酸 ２．０ｍｇ／モルＡｇＸ
安定剤：ＳＴＡＢ−１ ２×１０^−４モル／モルＡｇＸ
安定剤：ＳＴＡＢ−２ ２×１０^−４モル／モルＡｇＸ
安定剤：ＳＴＡＢ−３ ２×１０^−４モル／モルＡｇＸ
安定剤：ＳＴＡＢ−４ １×１０^−４モル／モルＡｇＸ
増感色素：ＲＳ−１ ２×１０^−４モル／モルＡｇＸ
増感色素：ＲＳ−２ ２×１０^−４モル／モルＡｇＸ
強色増感剤：ＳＳ−１ ２×１０^−４モル／モルＡｇＸ
上記調製したＥｍ−Ｒ１０１とＥｍ−Ｒ１０２の１：１の混合物を赤感光性ハロゲン化銀乳剤として使用した。
【０２０５】
【化３０】

【０２０６】
次いで、上記試料１０１の作製において、第７層で用いたＹカプラー（Ｙ−１）を等モルの（ＹＣ−３）、（ＹＣ−１４）、（ＹＣ−１６）に、第３層で用いたＭカプラー（Ｍ−１）を等モルの（ＭＣ−２）、（ＭＣ−７）、（ＭＣ−１７）に、第５層で用いたＣカプラー（Ｃ−１）を等モルの（ＣＣ−５）、（ＣＣ−７）、（ＣＣ−９）、（ＣＣ−１２）に、それぞれ表２に記載の組み合わせで置き換えた以外は同様にして、試料１０２〜１０８を作製した。
【０２０７】
《露光、現像処理》
（露光）
上記作製した各試料を２部用意し、一部は冷凍保存し、もう一部は５０℃、４０％ＲＨの条件下に１週間放置し、この試料がＣＩＥＬＡＢ色空間で（ａ^＊、ｂ^＊）＝（青：２６．５、−５３．０）、（緑：−６３．０、２２．０）、（赤：６５．５、４８．５）となるように各試料について露光条件を求め、網点％が４０％、５０％、６０％、７０％、８０％、１００％（ベタ）のパッチを露光し、下記の条件により現像処理を行った。
【０２０８】
露光装置としては、下記に示す装置を用意した。
光源としてＢのＬＥＤを主走査方向に５個並べ露光のタイミングを少しづつ遅延させることによって同じ場所を５個のＬＥＤで露光出来るように調整した。また、副走査方向にも２０個のＬＥＤを並べ隣接する２０画素分の露光が１度に出来る露光ヘッドを準備した。Ｇ、Ｒも同様にＬＥＤを組み合わせて露光ヘッドを準備した。各ビームの径は約１０μｍで、この間隔でビームを配列し、副走査のピッチは約２００μｍとした。
【０２０９】
（現像処理）
露光を施した各試料について、下記に示す現像処理を行った。
【０２１０】
なお、現像処理は、発色現像開始液での処理と、別途用意した補充液の総補充液量が、発色現像タンクの容量に等しくなるまでランニング処理を行った液の両方で処理を行った。
【０２１１】
処理工程 処理温度 時間 補充量
発色現像 ３７．０±０．３℃ １２０秒 ２００ｍｌ／ｍ^２
漂白定着 ３７．０±０．５℃ ９０秒 １５０ｍｌ／ｍ^２
安定化 ３０〜３４℃ ６０秒 ４００ｍｌ／ｍ^２
乾燥 ６０〜８０℃ ３０秒
〈発色現像液開始液及び補充液〉

水を加えて全量を１リットルとし、タンク液はｐＨ＝１０．２に、補充液はｐＨ＝１０．５に調整した。
【０２１２】
〈漂白定着液タンク液及び補充液〉
ジエチレントリアミン五酢酸第二鉄アンモニウム２水塩 ６５ｇ
ジエチレントリアミン五酢酸 ３ｇ
チオ硫酸アンモニウム（７０％水溶液） １００ｍｌ
２−アミノ−５−メルカプト−１，３，４−チアジアゾール ２．０ｇ
亜硫酸アンモニウム（４０％水溶液） ２７．５ｍｌ
水を加えて全量を１リットルとし、炭酸カリウム又は氷酢酸でｐＨ＝５．０に調整した。
【０２１３】
〈安定化液タンク液及び補充液〉
ｏ−フェニルフェノール １．０ｇ
５−クロロ−２−メチル−４−イソチアゾリン−３−オン ０．０２ｇ
２−メチル−４−イソチアゾリン−３−オン ０．０２ｇ
ジエチレングリコール １．０ｇ
蛍光増白剤（チノパールＳＦＰ） ２．０ｇ
１−ヒドロキシエチリデン−１，１−ジホスホン酸 １．８ｇ
硫酸亜鉛 ０．５ｇ
硫酸マグネシウム・７水塩 ０．２ｇ
ＰＶＰ（ポリビニルピロリドン） １．０ｇ
アンモニア水（水酸化アンモニウム２５％水溶液） ２．５ｇ
ニトリロ三酢酸・三ナトリウム塩 １．５ｇ
水を加えて全量を１リットルとし、硫酸又はアンモニア水でｐＨ＝７．５に調整した。
【０２１４】
《画像評価》
以上により得られた試料は、ミノルタ社製分光測色計ＣＭ−２０２２を用い、照明と受光の幾何条件ｄ−０、キセノンパルス光源を用いて測光し、２°視野補助標準の光Ｄ５０でのＬ^＊ａ^＊ｂ^＊の値を求めた。次いで、最小二乗法により（０、０）の点を通る直線で近似し、下記式１で表されるＧＯＦ値を求めた。
【０２１５】
【数１】

【０２１６】
ここで、
α：最小二乗法によって求められる係数
ａｉ：測定されたａ^＊の値
ｂｉ：測定されたｂ^＊の値
ｂｃａｌ：下記式により計算されたｂ^＊の値
ｂｃａｌ＝α×ａｉ
ｉ：１〜６の整数で、網点％が４０％、５０％、６０％、７０％、８０％、１００％の各測定値を示す
但し、青の評価を行う際には、ａｃａｌ＝α′×ｂｉでａ^＊の値を推定する形でＧＯＦ値を定義した。
【０２１７】
ランニング処理後の現像液で処理した試料から求めたＧＯＦ値１と発色現像開始液で処理した試料から求めたＧＯＦ値２の差（ΔＧＯＦ値）を求め、この結果を表２に示した。
【０２１８】
【表２】

【０２１９】
ＧＯＦ値は等色相線からのずれの標準偏差に相当する量であり、平均としてみた色相の揺らぎを表す量ということができる。このため、青とその他の色では最小二乗法で推定する式のａ^＊、ｂ^＊を入れ替えた。
【０２２０】
比較試料１０１では、冷凍保存試料の現像開始液でのＧＯＦ値１は、１．３〜２．０であり、ランニング処理後の処理液によって処理した結果でもΔＧＯＦ値は１．０〜１．８の劣化しか見られなかったが、５０℃、４０％ＲＨの雰囲気下で保存した試料においては、現像開始液ではＧＯＦ値２は、１．５〜１．９であったのに対し、ランニング処理後の処理液によって処理したΔＧＯＦ値は２．９〜３．８の劣化が見られた。（ΔＧＯＦ値は表２に示した。）本発明の試料においては、５０℃、４０％ＲＨの雰囲気下で保存した試料においても、ランニング処理後の処理液で処理した場合にも変動が小さいことが分かる。データを詳細にみると、本発明に用いられるカプラーと比較のカプラーとを同じ感光材料の中で使っている試料では、本発明に用いられるカプラー同士を組み合わせた色では比較的良好な結果となっており、カプラーに関わる因子の影響が大きいものと推察される。
【０２２１】
実施例２
実施例１で作製した試料１０１〜１０８において、イエロー画像形成ユニット、マゼンタ画像形成ユニットに使用した高沸点溶媒を、それぞれ等質量のジ−（２−エチルヘキシル）フタレートに置き換えて試料２０１〜２０８を作製した。
【０２２２】
更に、上記試料２０８において、シアン画像形成ユニットの高沸点溶媒を例示化合物（ＨＢＳ−１）、（ＨＢＳ−２）にそれぞれ変更した以外は同様にして、試料２０９〜２１０を作製した。
【０２２３】
また、試料２０８において、イエロー画像形成ユニットの高沸点溶媒をトリ−（２−エチルヘキシル）ホスフェートに置き換えた以外同様にして試料２１１を作製した。
【０２２４】
また、試料２０８において、マゼンタ画像形成ユニットの高沸点溶媒をトリ−（２−エチルヘキシル）ホスフェートとオレイルアルコールの等量混合物に置き換えた以外同様にして試料２１２を作製した。なお、高沸点溶媒（ＳＯ−４）、（ＳＯ−５）の混合物の比誘電率は、６．１０であった。これらの試料を実施例１と同様に評価し、得られたΔＧＯＦ値を表３に示した。
【０２２５】
【表３】

【０２２６】
表３より明らかなように、イエロー画像形成ユニット、マゼンタ画像形成ユニットに用いる高沸点溶媒として、ジ−（２−エチルヘキシル）フタレートを用いた試料でも、実施例１と同様に本発明の効果を得ることができ、５０℃、４０％ＲＨの雰囲気下で保存した試料においても、現像開始液と、ランニング処理後の現像液での色相のズレは小さくなることが分かる。しかし、表２と表３を比較すると、イエロー画像形成ユニットにトリオクチルホスフィンオキサイド（ＳＯ−１）やトリ−（２−エチルヘキシル）ホスフェートを用いた試料で、その効果が大きいことが分かる。また表３から、マゼンタ画像形成ユニットでオレイルアルコールとトリオクチルホスフィンオキサイド（ＳＯ−１）またはトリー（２−エチルヘキシル）ホスフェートを併用したもの、シアン画像形成ユニットで（ＨＢＳ−１）、（ＨＢＳ−２）を用いた試料で、その効果が大きいことが分かった。
【０２２７】
実施例３
実施例１で画像作成した試料１０１の赤、緑、青の網点％が４０％、５０％、６０％、７０％、８０％、１００％のパッチの濃度を測定し、この濃度に対応する画像データと自然画像、ポートレート画像を編集した画像データを用意した。
【０２２８】
実施例１で用いた露光装置により、この各画像を実施例１の試料１０１〜１０３（冷凍保存と５０℃、４０％ＲＨで保存した試料）に出力し、現像開始液とランニング処理後の現像液とで各々実施例１に記載の方法で現像処理を行った。
【０２２９】
次いで、実施例１と同様の方法で、カラーパッチ部分のΔＧＯＦ値を測定し、得られた結果を表４に示した。
【０２３０】
【表４】

【０２３１】
画像データが異なっているなどの影響により結果に少しズレはあるものの、本発明の効果が得られていることが確かめられた。
【０２３２】
次ぎに、同じ画像を一辺が１５０μｍの画素で読み込み、これを一辺が１０μｍの画素のデータに変換するに際して、１０μｍの無色（白）の縁を有し、その内部が一定濃度であるような画像データに変換させた。このデータをＲＩＰ処理し、実施例１で用いた露光装置によりこの画像を実施例１の試料１０１〜１０３（冷凍保存と５０℃４０％保存試料）に出力し、現像開始液とランニング処理後の現像液とで各々処理を行いカラー画像を得た。
【０２３３】
この画像を、実施例１と同様にしてカラーパッチ部分のΔＧＯＦ値を測定し、得られた結果を表５に示した。
【０２３４】
【表５】

【０２３５】
この画像は、微細な網目構造をもった画像であるが、基本的には濃度変調画像である。表５の結果と表４の結果を比べると、色相の変動は濃度変調画像で作成した場合の方が小さくなることが分かる。
【０２３６】
また、自然画像とポートレートで２つの出力方式の画質の相違を見ると、濃度変調によって作成した画像の方が、特に、ポートレートの肌の滑らかな再現に優れていることが確認できた。
【０２３７】
実施例４
実施例１の評価を、前記露光装置が、デジタル画像情報とデバイスに依存しない画像データとを対応づける印刷条件プロファイル、及び前記デバイスに依存しない画像データと露光用画像データとを対応づける露光条件プロファイルとに基づいて、前記デジタル画像情報を前記露光用デジタル画像データに変換する色変換手段をもたせた以外同様にして、試料１０１〜１０３を用いて、ΔＧＯＦ値の測定を行い、得られた結果を表６に示した。
【０２３８】
【表６】

【０２３９】
表６より明らかなように、保存前の試料で露光条件プロファイルを作成することによって、冷凍保存の試料では、比較試料においても色相のズレは大幅に改善されるが、５０℃４０％で保存した試料の場合には、色相のズレは改良されずむしろ若干大きめになっていた。一方、本発明試料においては、冷凍保存の試料で改良されるのはもちろん、５０℃４０％保存においても色相のズレはより小さくなっていた。本発明において、このようなカラーマネージメントシステムの適用は、より好ましい実施態様である。
【０２４０】
上記と同様の評価を、実施例３の微細な網目構造をもった濃度変調画像について行った結果を表７に示す。
【０２４１】
【表７】

【０２４２】
表７より明らかなように、面積変調画像と同様に比較試料においても色相のズレは大幅に改善されるが、本発明の試料がより優れた特性を示すことが分かる。
【０２４３】
実施例５
実施例１に記載の発色現像液で用いた発色現像主薬であるＮ−エチル−Ｎ−（β−ヒドロキシエチル）−４−アミノアニリン硫酸塩を、等モルの例示化合物ＣＤ−６に変えた以外同様にして試料１０１〜１０３を用いて、ΔＧＯＦ値の測定を行い、得られた結果を表８に示す。
【０２４４】
【表８】

【０２４５】
表８より明らかなように、例示化合物ＣＤ−６を含む発色現像液を用いた系においても、上記実施例と同様に本発明の効果が得られることがわかる。また、表２の結果と比較するとＣＤ−６を用いた発色現像液により、保存後の試料であってもより安定した試料が得られることが分かった。
【０２４６】
【発明の効果】
本発明により、２次色の網点％の変化による連続現像処理前後での色相変動が小さいプルーフ画像を、ハロゲン化銀感光材料の保存状態によらず安定して形成することができた。
【図面の簡単な説明】
【図１】本発明の画像データを露光用のデータに編集していく処理作業のフローチャートである。
【図２】本発明の処理作業を示すブロック図である。[0001]
TECHNICAL FIELD OF THE INVENTION
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a proof for confirming the finish of a printed matter in advance, and more particularly, to a proof image having a small hue change in a continuous development process (running process) due to a change in halftone dot% of a secondary color. The present invention relates to a color image forming method which can be stably obtained regardless of the storage state of a photosensitive material.
[0002]
[Prior art]
Silver halide light-sensitive materials (hereinafter, also simply referred to as light-sensitive materials) are widely used today because of their high sensitivity, excellent color reproducibility, and suitability for continuous processing. Due to these characteristics, silver halide photosensitive materials are used not only in the field of general photography for photography but also in the field of printing, especially in the field of so-called proofing for checking the state of the finished printed matter during printing. It is becoming widely used.
[0003]
In the field of proofing, an image edited on a computer is output on a printing film, and the developed film is appropriately exposed and separated and exposed, so that yellow (Y), magenta (M), and cyan (C) are obtained. By forming each image and forming an image of the final printed matter on color photographic paper, it has been performed to judge the suitability of the layout and color of the final printed matter.
[0004]
Recently, a method of outputting an image edited on a computer directly to a printing plate has gradually become widespread. In such a case, a color image can be obtained directly from data on the computer without using a film. Is desired.
[0005]
For this purpose, various methods such as sublimation type / fusion heat transfer method, electrophotographic method, and ink jet method have been tried, but the method of obtaining high quality images is expensive and the productivity is inferior. On the contrary, there is a drawback that the image quality is inferior in the system which is low in cost and high in productivity.
[0006]
In contrast to the above problems, a system using a silver halide light-sensitive material enables high-quality image formation such as accurate halftone dot image formation due to excellent sharpness and the like. In addition, high productivity can be realized because the above-described processing is possible and images can be written to a plurality of color image forming units at the same time.
[0007]
In recent years, in the field of printing, so-called digitization has progressed, and there has been an increasing demand for obtaining images directly from data in a computer. For the reasons described above, silver halide photosensitive materials have begun to be advantageously used in this field.
[0008]
A system that forms an area-modulated image based on digital data divides a halftone dot into smaller units (here, these are expressed as pixels), and exposes the pixels with an appropriate exposure amount to form an aggregate. It is possible to reproduce halftone dots. As a simple example, if one halftone dot is composed of 100 pixels, 50% of the halftone dots are converted to 50% halftone dots by exposing 50 pixels so as to be developable. Can be formed. Normally, in printing, when the dot percentage changes, a in the CIELAB color space^*b^*Although the points move almost linearly in the plane, the system using silver halide photosensitive material, especially using a silver halide photosensitive material that has been stored for a long time, and further depending on the processing amount of the developed silver halide photosensitive material When evaluation is performed in a so-called running processing state in which development processing is continuously performed while replenishing an appropriate processing solution, there is a drawback that hue variation is likely to occur due to a change in dot percentage.
[0009]
However, in a silver halide photosensitive material that forms an area-modulated image based on four pieces of image information of yellow, magenta, cyan, and black, the dot percentage of the black or 4-color black image is 40, 50, 60, 70, 80. , 100% of 6 points in CIELAB color space a^*, B^*When a locus in a plane is approximated to a straight line passing through the origin, a silver halide photosensitive material having excellent linearity is disclosed (for example, see Patent Document 1). It discloses that such a silver halide photosensitive material gives an impression that the color tone of the black is stable and the reproduction of the black is tight, and is excellent in the reproduction of the black. Further, although a structure similar to the structure of the present application is disclosed as the structure of the coupler, considering that the reproduction of black, that is, the neutral gray is affected by the details of the structure of the three types of couplers, the structure of the coupler according to the present application is considered. No mention is made of the superior structure or the phenomenon that the linearity is degraded due to long-term storage of the photosensitive material.
[0010]
Further, in order to obtain an image similar to the standard image using a silver halide photosensitive material, the chromaticity of the black plate whose halftone dot% is 50% is ΔEab^*≦ 1.3 and a in the CIELAB color space of 6 points of 40%, 50%, 60%, 70%, 80%, and 100% halftone dot% of the black plate image^*, B^*An image forming method in which a locus in a plane approximates a straight line is disclosed (for example, refer to Patent Document 2). When this condition is satisfied, it is possible to suppress the occurrence of a phenomenon that causes an unnatural contour in an image having a smooth gradation. However, in these disclosed methods, there is no mention of deterioration in linearity due to long-term storage of the photosensitive material.
[0011]
Furthermore, the silver halide light-sensitive material is separately subjected to single-color exposure with a reference light amount to obtain a relationship between the exposure amount and the separated color density, and by controlling the separated color density, image formation that ensures color reproducibility against fluctuations. A method is disclosed (for example, see Patent Document 3). According to the description of the example of Patent Document 3, it is disclosed that the relationship between the exposure amount and the decomposed color density is obtained by performing monochromatic exposure, and that the performance variation of the photosensitive material can be appropriately compensated by performing this correction. The relationship between the exposure amount and the decomposition color density corresponds to the relationship between the exposure amount and the amount corresponding to the amount of the image dye of the present invention. Patent Document 3 describes the characteristics of the photosensitive material as the exposure amount and the decomposition color density. The disclosure of what kind of processing can be performed when the characteristics fluctuate can be compensated for by giving it as. Nothing is said. According to the present invention, in addition to the data on the characteristics of the photosensitive material, the relationship between the color of the pixel (the minimum unit of exposure constituting a halftone dot) and the amount corresponding to the amount of the image dye is provided as data. This is a method related to the method of determining the image forming conditions, which makes it easy to respond to changes in the spectral absorption of the coloring material of the recording material, etc., and also to meticulously respond to user preferences and differences in printing conditions. Only a part of this system is disclosed in the above publication.
[0012]
[Patent Document 1]
Japanese Patent Application Laid-Open No. 2000-267235 (Claims, Claim 4)
[0013]
[Patent Document 2]
JP 2001-209153 A (Claims, Claim 4)
[0014]
[Patent Document 3]
JP-A-2002-365745 (Claims, Claim 4)
[0015]
[Problems to be solved by the invention]
SUMMARY OF THE INVENTION It is an object of the present invention to provide a color image capable of stably obtaining a proof image having a small hue variation before and after continuous development processing due to a change in the dot percentage of a secondary color, regardless of the storage state of the silver halide photosensitive material. It is to provide a forming method.
[0016]
[Means for Solving the Problems]
The present inventors have conducted intensive studies in view of the above problems, and as a result, have found that the above objects of the present invention can be achieved by the following constitutions, and have completed the present invention.
[0017]
1. A silver halide light-sensitive material having at least one yellow image forming unit, magenta image forming unit, and cyan image forming unit on a support has a resolution of 1000 dpi (dots per 2.54 cm) or more. In a color image forming method by area modulation in which an image is exposed by an exposure device capable of changing image density and then developed with a color developing solution containing a color developing agent, the yellow image forming unit is represented by the general formula (I). The magenta image forming unit contains the compound represented by the general formula (II), and the cyan image forming unit contains the compound represented by the general formula (III), the general formula (IV) and the general formula (V) ) And a compound selected from the general formula (VI).
[0018]
2. A silver halide photosensitive material having at least one yellow image forming unit, magenta image forming unit, and cyan image forming unit on a support is exposed by an exposure device having a resolution of 1000 dpi or more and capable of changing the image density. After that, in a color image forming method by area modulation in which development processing is carried out with a color developing solution containing a color developing agent, the yellow image forming unit comprises a compound represented by the general formula (I) and a phosphate or phosphine oxide compound. Wherein the magenta image forming unit contains a compound represented by the general formula (II), an alcohol compound having 10 or more carbon atoms and a phosphate or phosphine oxide compound, and the cyan image forming unit contains The compound represented by the general formula (III) has a relative dielectric constant of 6 or more. Color image forming method characterized by containing the point organic solvent.
[0019]
3. A silver halide photosensitive material having at least one yellow image forming unit, magenta image forming unit, and cyan image forming unit on a support is exposed by an exposure device having a resolution of 1000 dpi or more and capable of changing the image density. A color image forming method based on area modulation in which a development process is performed with a color developing solution containing a color developing agent, wherein a density-modulated image is output as an image in which a specific pattern is superimposed on an original image. .
[0020]
4. The yellow image forming unit contains the compound represented by the general formula (I), the magenta image forming unit contains the compound represented by the general formula (II), and the cyan image forming unit contains the compound represented by the general formula (II). 4. The color image forming method according to the above item 3, wherein the method comprises the compound represented by (III).
[0021]
5. The exposure apparatus, based on a print condition profile that associates digital image information with device-independent image data, and an exposure condition profile that associates device-independent image data with exposure digital image data, The color image forming method according to any one of claims 1 to 4, further comprising a color conversion unit configured to convert image information into the digital image data for exposure.
[0022]
6. The color developing agent is 4-amino-3-methyl-N-ethyl-N- (β- (methanesulfonamido) ethyl) aniline, any one of the above-mentioned items 1-3. Color image forming method.
[0023]
7. After exposing a silver halide photosensitive material having at least one yellow image forming unit, magenta image forming unit, and cyan image forming unit on a support by an exposure device having a resolution of 1000 dpi or more and capable of changing the image density, In a color image forming method by area modulation for development, the relationship between the amount of exposure to a silver halide photosensitive material and the amount corresponding to the amount of image dye and the relationship between the pixel color and the amount corresponding to the amount of image dye are used. 7. The color image forming method according to any one of the above items 1 to 6, wherein energy required for image formation is obtained.
[0024]
In the present invention, the term "yellow image forming unit" is used, which means a layer for forming a yellow dye image, or a layer group for forming a yellow dye image, and most simply, a yellow coupler-containing silver halide emulsion layer. When two or more silver halide emulsion layers containing a yellow coupler are included, these are collectively referred to as a yellow image forming unit. When the photosensitive layer has a photosensitive layer, these two layers are collectively referred to as a yellow image forming unit. Even if a yellow coupler is contained, for example, a magenta coupler is also contained, and the maximum color density is defined as a in the CIELAB color space.^*b^*If the hue angle in the plane does not fall within the range of 45 ° to 135 °, it is not defined as a yellow image forming unit. The magenta image forming unit and the cyan image forming unit can be defined similarly.
[0025]
As the silver halide emulsion used in the present invention, a silver halide emulsion comprising 95% by mole or more of silver chloride is preferable, and any halogen such as silver chloride, silver chlorobromide, silver chloroiodobromide and silver chloroiodide can be used. Those having a composition are used. Among them, a silver chlorobromide containing 95 mol% or more of silver chloride, particularly a silver halide emulsion having a portion containing silver bromide in a high concentration is preferably used. Silver chloroiodide containing about 0.5 mol% is also preferably used. In the silver halide emulsion having a portion containing silver bromide at a high concentration, the portion containing silver bromide at a high concentration may be a so-called core-shell emulsion or may be simply formed without forming a complete layer. A so-called epitaxy junction region in which only a region having a partially different composition may exist may be formed. It is particularly preferable that the portion where silver bromide exists at a high concentration is formed at the top of crystal grains on the surface of silver halide grains. Further, the composition may change continuously or may change discontinuously.
[0026]
It is advantageous that the negative working silver halide emulsion used in the present invention contains a heavy metal ion. This is expected to improve the so-called reciprocity failure and prevent desensitization in high-illuminance exposure and softening on the shadow side (shaded area). Examples of heavy metal ions that can be used for such purposes include iron, iridium, platinum, palladium, nickel, rhodium, osmium, ruthenium, cobalt and other Group 8 to 10 metals, and cadmium, zinc and mercury. Examples thereof include Group 12 transition metals and ions of lead, rhenium, molybdenum, tungsten, gallium, and chromium. Among them, metal ions of iron, iridium, platinum, ruthenium, gallium, and osmium are preferable. These metal ions can be added to the silver halide emulsion in the form of a salt or a complex salt. When the heavy metal ion forms a complex, as the ligand, for example, cyanide ion, thiocyanate ion, cyanate ion, chloride ion, bromide ion, iodide ion, carbonyl, nitrosyl, ammonia, Examples thereof include 1,2,4-triazole and thiazole. Among them, chloride ion, bromide ion and the like are preferable. These ligands may be used alone or in combination of a plurality of ligands.
[0027]
These metal compounds can also be characterized as the depth of electron traps when contained in silver halide emulsion grains. Examples of the compound that gives a shallow electron trap having a depth of 0.2 eV or less include a second lead ion or a compound having a cyano ligand, which is effective for improving reciprocity failure, particularly low illumination failure. . In addition, examples of the compound that gives a deep electron trap having a depth of 0.35 eV or more include Ir, Rh, and Ru compounds having a halide ion or a nitrosyl ligand. These compounds can be preferably used for improving high-illuminance reciprocity failure. It is also a preferable embodiment to use a compound that gives a shallow electron trap with a depth of 0.2 eV or less and a compound that gives a deep electron trap with a depth of 0.35 eV or more. These compounds are described in detail in pages 4 to 5 of JP-A-2000-214561.
[0028]
In order to make the silver halide emulsion contain heavy metal ions, the heavy metal compound is added before forming silver halide grains (hereinafter also simply referred to as grains), during formation of silver halide grains, or after forming silver halide grains. What is necessary is just to add in arbitrary places of each process during physical ripening.
[0029]
The heavy metal compound can be dissolved together with the halide salt and added continuously over the whole or a part of the grain forming step. Alternatively, it can be prepared by forming silver halide fine particles containing these heavy metal compounds in advance and adding them. The amount of the heavy metal ion added to the silver halide emulsion is 1 × 10 5 per mol of silver halide.^-91 x 10 or more^-2Mol or less, more preferably 1 × 10^-85 x 10 or more^-5Molar or less is preferred.
[0030]
The particles used in the present invention may have any shape. One preferable example is a cube having a [100] plane as a crystal surface. Also, U.S. Pat. Nos. 4,183,756 and 4,225,666, JP-A-55-26589, JP-B-55-42737, and The Journal of Photographic Science (J. Photogr. Sci., No. 21, p. 39 (1973), etc., can be used to produce particles having shapes such as octahedron, tetradecahedron, and dodecahedron, and to use these. . Further, particles having a twin plane may be used.
[0031]
As the grains used in the present invention, grains having a single shape are preferably used, and it is particularly preferable to add two or more kinds of monodispersed silver halide emulsions to the same layer.
[0032]
The particle size of the particles used in the present invention is not particularly limited, but is preferably from 0.1 to 1.2 μm, more preferably from 0.2 to 1.2 μm in consideration of other photographic properties such as rapid processing property and sensitivity. The range is 1.0 μm.
[0033]
This particle size can be measured using the projected area or diameter approximation of the particle. If the particles are substantially uniform in shape, the particle size distribution can represent this fairly accurately as diameter or projected area.
[0034]
The particle size distribution of the silver halide grains used in the present invention is preferably a monodispersed silver halide grain having a variation coefficient of 0.22 or less, more preferably 0.15 or less, and particularly preferably a variation coefficient of 0 or less. .15 or less is added to the same layer. Here, the variation coefficient is a coefficient representing the width of the particle size distribution, and is defined by the following equation.
[0035]
Coefficient of variation = S / R
(Where S represents the standard deviation of the particle size distribution and R represents the average particle size).
Various methods known in the art can be used as a method and apparatus for preparing a silver halide emulsion.
[0036]
The silver halide emulsion used in the present invention may be obtained by any of an acidic method, a neutral method, and an ammonia method. The silver halide grains may be grown at a time or may be grown after seed grains have been formed. The method for producing the seed particles and the method for growing the seed particles may be the same or different.
[0037]
The form of reacting the soluble silver salt with the soluble halide salt may be any method such as a forward mixing method, a reverse mixing method, a simultaneous mixing method, or a combination thereof, but the method obtained by the simultaneous mixing method is preferable. . Further, as one type of the double jet method, a pAg controlled double jet method described in JP-A-54-48521 can also be preferably used.
[0038]
JP-A-57-92523 and JP-A-57-92524 disclose an apparatus for supplying an aqueous solution of a water-soluble silver salt and a water-soluble halide salt from an addition apparatus disposed in a reaction mother liquor. , 921, 164, etc. for continuously adding an aqueous solution of a water-soluble silver salt and a water-soluble halide salt in a concentration-variable manner, and adding a reaction mother liquor to the outside of a reactor described in JP-B-56-501776. An apparatus may be used in which the silver halide grains are taken out and concentrated by ultrafiltration to form grains while keeping the distance between the silver halide grains constant.
[0039]
Further, if necessary, a silver halide solvent such as thioether may be used. Further, a compound having a mercapto group, a nitrogen-containing heterocyclic compound or a compound such as a sensitizing dye may be added at the time of forming silver halide grains or after the completion of grain formation.
[0040]
The negative-working silver halide emulsion used in the present invention can be used in combination with a sensitization method using a gold compound and a sensitization method using a chalcogen sensitizer. Examples of the chalcogen sensitizer include a sulfur sensitizer, a selenium sensitizer, and a tellurium sensitizer, and a sulfur sensitizer is preferable. Examples of the sulfur sensitizer include thiosulfate, triethylthiourea, allylthiocarbamide thiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate, rhodanine, and inorganic sulfur.
[0041]
The addition amount of the sulfur sensitizer is preferably changed depending on the kind of the silver halide emulsion to be applied, the size of the expected effect, and the like.^-10~ 5 × 10^-5Molar range, preferably 5 × 10^-8~ 3 × 10^-5A molar range is preferred.
[0042]
As the gold sensitizer, for example, chloroauric acid, gold sulfide and the like, and various gold complexes can be added. Examples of the ligand compound used include dimethyl rhodanine, thiocyanic acid, mercaptotetrazole, mercaptotriazole and the like. The amount of the gold compound used is not uniform depending on the type of the silver halide emulsion, the type of the compound to be used, the ripening conditions, and the like, but is usually 1 × 10 5 per mol of the silver halide.^-4~ 1 × 10^-8Preferably it is molar. More preferably 1 × 10^-5~ 1 × 10^-8Is a mole. These compounds can be added not only as a sensitizer but also for various purposes at the stage of preparing a coating solution. Further, as the chemical sensitization method for the negative-working silver halide emulsion used in the present invention, a reduction sensitization method may be used.
[0043]
The silver halide emulsion used in the present invention may be any of known silver halide emulsions for the purpose of preventing fog occurring during the step of preparing a silver halide light-sensitive material, reducing performance fluctuation during storage, and preventing fog occurring during development. Antifoggants and stabilizers can be used. Preferred examples of the compound that can be used for such a purpose include a nitrogen-containing heterocyclic mercapto compound represented by the general formula (II) described in the lower section of page 7 of JP-A-2-14636, More preferred specific compounds include compounds (IIa-1) to (IIa-8) and (IIb-1) to (IIb-7) described on page 8 of the same publication, and JP-A-2000-267235. On page 8, right column, lines 32-36. These compounds are added according to the purpose in the steps of preparing silver halide emulsion grains, chemical sensitizing step, finishing the chemical sensitizing step, and preparing a coating solution. When chemical sensitization is performed in the presence of these compounds, 1 × 10 5^-5~ 5 × 10^-4It is preferably used in a molar amount. When added at the end of chemical sensitization, 1 × 10^-6~ 1 × 10^-2Molar amounts are preferred, and 1 × 10^-5~ 5 × 10^-3Molar is more preferred. In the step of preparing a coating solution, when adding to the silver halide emulsion layer, 1 × 10^-6~ 1 × 10^-1Molar amounts are preferred, and 1 × 10^-5~ 1 × 10^-2Molar is more preferred. When added to a layer other than the silver halide emulsion layer, the amount in the coating film is 1 m²1 × 10 per^-9~ 1 × 10^-3Molar amounts are preferred.
[0044]
Other additives can be added to the silver halide emulsion used in the present invention for various purposes. For example, disulfides and polysulfide compounds such as A-20, C-1, C-9, C-14, C-15, C-16 and C-40 specifically described in JP-A-2-14636, It is preferable to use thiosulfonic acid compounds such as D-1, D-3, D-6 and D-8, inorganic sulfur and the like.
[0045]
In the silver halide light-sensitive material according to the present invention, dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and halation. For this purpose, any of the known compounds can be used. In particular, as dyes having absorption in the visible region, dyes of AI-1 to 11 described in JP-A-3-251840, page 308, and dyes having an absorption in the visible region can be used. The dyes described in JP-A-3770 are preferably used.
[0046]
The silver halide light-sensitive material according to the present invention comprises a hydrophilic colloid colored with at least one layer of a diffusion-resistant compound on the side closer to the support than the silver halide emulsion layer closest to the support among the silver halide emulsion layers. It is preferred to have a layer. As the coloring substance, a dye or another organic or inorganic coloring substance can be used.
[0047]
The silver halide light-sensitive material according to the present invention may have at least one colored hydrophilic colloid layer closer to the support than the silver halide emulsion layer closest to the support among the silver halide emulsion layers. Preferably, the hydrophilic colloid layer may contain a white pigment, for example, using rutile-type titanium dioxide, anatase-type titanium dioxide, barium sulfate, barium stearate, silica, alumina, zirconium oxide, kaolin, or the like. Of these, titanium dioxide is preferred among others for various reasons. The white pigment is dispersed in an aqueous binder of, for example, a hydrophilic colloid such as gelatin so that the treatment liquid can penetrate. The coating amount of the white pigment is preferably 0.1 to 50 g / m.²And more preferably 0.2 to 5 g / m²Range.
[0048]
Between the support and the silver halide emulsion layer closest to the support, in addition to the above-mentioned white pigment-containing layer, if necessary, a non-photosensitive hydrophilic layer such as an undercoat layer or an intermediate layer at an arbitrary position. An aqueous colloid layer can be provided.
[0049]
In the silver halide light-sensitive material according to the present invention, whiteness can be further improved by adding a fluorescent whitening agent, which is preferable. The fluorescent whitening agent is not particularly limited as long as it can absorb ultraviolet light and emit visible light fluorescence, but a diaminostilbene compound having at least one sulfonic acid group in the molecule is preferable. These compounds also have the effect of promoting the elution of the sensitizing dye out of the light-sensitive material. Another preferred embodiment is a solid particulate compound having a fluorescent whitening effect.
[0050]
The silver halide light-sensitive material according to the present invention has a layer containing a silver halide emulsion spectrally sensitized to a specific region in a wavelength region of 400 to 900 nm. The silver halide emulsion contains one or more sensitizing dyes in combination.
[0051]
As the spectral sensitizing dye used in the silver halide emulsion used in the present invention, any known compounds can be used. Examples of the blue sensitizing dye include those described in JP-A-3-251840, page 28. BS-1 to BS-8 can be preferably used alone or in combination. As the green photosensitive sensitizing dye, GS-1 to GS-5 described on page 28 of the same publication are preferably used. As red-sensitive sensitizing dyes, RS-1 to RS-8 described on page 29 of the publication are preferably used.
[0052]
These sensitizing dyes may be added at any time from the formation of silver halide grains to the end of chemical sensitization. In addition, as a method for adding these dyes, water or an organic solvent miscible with water such as methanol, ethanol, fluorinated alcohol, acetone, and dimethylformamide may be dissolved and added as a solution. May be added as a solution, emulsion or suspension in a water-miscible solvent having a density of more than 1.0 g / ml.
[0053]
As a method of dispersing the sensitizing dye, a method of mechanically pulverizing and dispersing the sensitizing dye into fine particles having a particle size of 1 μm or less in an aqueous system using a high-speed stirring dispersing machine may be used, as described in JP-A-58-105141. 8, a method of mechanically pulverizing and dispersing into fine particles of 1 μm or less in an aqueous system under the conditions of 60 to 80 ° C., the surface tension of 3.8 × 10 described in JP-B-60-6496.^-2A method of dispersing in the presence of a surfactant suppressed to not more than N / m, dissolving in an acid substantially free of water and having a pKa not exceeding 5 as described in JP-A-50-80826, A method of adding and dispersing in an aqueous liquid and adding this dispersion to a silver halide emulsion can be used.
[0054]
Water is preferable as a dispersion medium used for dispersion, but the solubility may be adjusted by adding a small amount of an organic solvent, or the stability of the dispersion may be increased by adding a hydrophilic colloid such as gelatin.
[0055]
Examples of the dispersing device that can be used for preparing the dispersion include, for example, a high-speed stirring type dispersing device shown in FIG. 1 of JP-A-4-125563, a ball mill, a sand mill, an ultrasonic dispersing device, and the like. Can be mentioned. When using these dispersing apparatuses, a method may be used in which pretreatment such as dry pulverization is performed in advance and then wet dispersing is performed, as described in JP-A-4-125632.
[0056]
The silver halide emulsion used in the present invention may contain one kind or a combination of two or more kinds of sensitizing dyes.
[0057]
As the coupler used in the silver halide light-sensitive material according to the present invention, any compound capable of forming a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm by coupling reaction with an oxidized form of a color developing agent is used. Although it is also possible to use, particularly typical examples include a yellow dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, a magenta dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 500 to 600 nm, Typical examples are cyan dye-forming couplers having a spectral absorption maximum wavelength in a wavelength range of 600 to 750 nm.
[0058]
One of the features of the invention according to claim 1 is that it contains the yellow coupler represented by the general formula (I).
[0059]
Hereinafter, the yellow coupler represented by Formula (I) will be described.
In the general formula (I), R₁₁Examples of the alkyl group represented by include groups such as methyl, ethyl, and i-propyl. R₁₁Examples of the diffusion-resistant group represented by are a long-chain alkyl group such as a dodecyl group, a hexadecyl group, and an octadecyl group.
[0060]
Y₁The diffusion-resistant group represented by is preferably a diffusion-resistant group bonded by an acylamino group, for example, palmitoylamino, stearoylamino, 2- (2,4-di-t-bentylphenoxy) butanoylamino group and the like. Each group of is mentioned.
[0061]
Z₁As the group capable of leaving by reaction with an oxidized developing agent bonded by a nitrogen atom represented by the following formula, a hydantoin nucleus, an oxazolidinedione nucleus and the like are preferably used.
[0062]
Λ of spectral absorption of a yellow image formed by the photosensitive material according to the present invention._maxIs preferably 425 nm or more._0.2Is preferably 515 nm or less. λL_0.2In the spectral absorbance curve of an image dye, when the maximum absorbance is 1.0, the wavelength is longer than the wavelength showing the maximum absorbance and the absorbance is 0.2. This amount is a measure that indicates the magnitude of unnecessary absorption on the long-wave side of the image dye, and λ_maxIt means that unnecessary absorption is smaller as the wavelength is closer to.
[0063]
Hereinafter, typical examples of the yellow coupler represented by the general formula (I) are shown, but the invention is not limited thereto.
[0064]
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[0065]
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[0066]
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[0067]
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[0068]
The yellow coupler according to the present invention is generally used in the silver halide emulsion layer in an amount of 1 × 10 5 per mol of silver halide.^-3~ 1 mol, preferably 1 × 10^-2~ 8 × 10^-1It can be used in the molar range.
[0069]
One of the features of the invention according to claim 1 is that it contains a magenta coupler represented by the general formula (II).
[0070]
Hereinafter, the magenta coupler represented by the general formula (II) will be described.
In the general formula (II), R₂₁The primary or secondary alkyl group represented by is preferably a methyl group, an iso-propyl group, a 2,2-dimethylpropyl group, or the like. As the arylamino group, an anilino group or the like is preferable, and as the alkoxy group, a 2-phenoxyethoxy group or the like is preferably used.
[0071]
R₂₂Examples of the straight-chain linking group having 3 or more carbon atoms represented by are substituted and unsubstituted trimethylene groups, and a 1,1-dimethylpropylene group and the like can also be preferably used.
[0072]
R₂₃The non-diffusible group represented by is preferably a long-chain alkyl group such as a dodecyl group, a hexadecyl group, an octadecyl group, or a non-diffusible group bonded by an acylamino group. For example, palmitoylamino, stearoylamino, 2- (2, Each group such as 4-di-t-bentylphenoxy) butanoylamino group is exemplified.
[0073]
J₂Of the groups represented by, preferred are-(C = O) -O-, -O- (C = O)-,-(C = O) -NH-, -NH- (C = O)-. , -Ph- (C = O) -NH-, -Ph-NH- (C = O)-, particularly preferably-(C = O) -O-,-(C = O) -NH-. is there.
[0074]
R₂₄~ R₂₇The alkyl group represented by preferably has 1 to 32 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a (t) butyl group, a hexyl group, an octyl group, a dodecyl group, a hexadecyl group, A typical example thereof is a 2-ethylhexyl group.
[0075]
R₂₄~ R₂₇The cycloalkyl group represented by is preferably a cycloalkyl group having 3 to 12 carbon atoms, and examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a 2-methylcyclopropyl group, and an adamantyl group.
[0076]
R₂₄~ R₂₇The aryl group represented by is preferably one having 6 to 14 carbon atoms, and typical examples thereof include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.
[0077]
R₂₄~ R₂₇The alkyl group, cycloalkyl group, and aryl group represented by may each have a substituent.
[0078]
R₂₄~ R₂₇As the group represented by, a hydrogen atom is more preferably used.
X₂Represents a group capable of leaving by reaction with an oxidized form of a color developing agent, and includes a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom, etc.), an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, Examples include a ring thio group and a nitrogen-containing heterocyclic ring bonded by an N atom (for example, a hydantoin nucleus, an oxazolidinedione nucleus, a urazole nucleus, and the like). R₂₁Is a primary or secondary alkyl group or an alkoxy group,₂Is preferably a halogen atom, particularly preferably a chlorine atom;₂₁Is an arylamino group, X₂Is preferably an arylthio group.
[0079]
Hereinafter, typical examples of the magenta coupler represented by the general formula (II) are shown, but the present invention is not limited thereto.
[0080]
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[0081]
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[0082]
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[0083]
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[0084]
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[0085]
The magenta coupler represented by the general formula (II) can be used in combination with another type of magenta coupler as long as the effects of the present invention are not impaired, and usually 1 × 10 5 per mol of silver halide.^-3~ 1 mol, preferably 1 × 10^-2~ 8 × 10^-1It can be used in the molar range.
[0086]
In the light-sensitive material according to the present invention, λ of the spectral absorption of the formed magenta image_maxIs preferably 530 to 560 nm, and λL_0.2Is preferably 580 to 635 nm.
[0087]
The magenta image forming layer of the silver halide light-sensitive material according to the present invention preferably contains a yellow coupler in addition to the magenta coupler. In the silver halide light-sensitive material according to the present invention, as a preferable yellow coupler to be contained in the magenta image-forming layer, a known pivaloylacetanilide-type or benzoylacetanilide-type coupler can be used. Specific examples of preferable yellow couplers to be contained in the magenta image-forming layer of the light-sensitive material according to the present invention are represented by YCP-1 to YCP-39 described in the right column of pages 6 to 15 of JP-A-8-314079. Couplers, of course, but are not limited to these.
[0088]
One of the features of the invention according to claim 1 is that it contains at least one selected from the cyan couplers represented by the general formulas (III) to (VI). Hereinafter, the cyan couplers represented by the general formulas (III) to (VI) will be described.
[0089]
In the general formula (III), Ar represents an aryl group or a heterocyclic group, and examples of the aryl group include a phenyl group and a naphthyl group. The heterocyclic group represented by Ar is preferably a 5- to 7-membered heterocyclic group, specifically, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl, 1-pyrrolyl, 1- Examples thereof include a tetrazonyl group.
[0090]
The aryl group and the heterocyclic group represented by Ar may further have a substituent, and these substituents are not particularly limited. Typical examples thereof include an alkyl group, an alkenyl group, an alkynyl group, An aryl group and a heterocyclic group can be exemplified. Ar is preferably a phenyl group.
[0091]
R₁Represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group;₁Examples of the alkyl group represented by include a methyl group, an ethyl group, an isopropyl group, a butyl group, a dodecyl group, a cyclohexyl group, and an adamantyl group. Examples of the alkynyl group include vinyl, allyl, oleyl, and cyclohexenyl groups. Examples of the alkenyl group include propargyl and 1-pentynyl. R₁An aryl group represented by₁Examples of the heterocyclic group represented by are groups having the same meaning as the group represented by Ar. R₁The alkyl group, alkenyl group, alkynyl group, aryl group, and heterocyclic group represented by may further have a substituent.
[0092]
The divalent linking group represented by L is preferably an alkylene group or an arylene group, and n represents 0 or 1, and is preferably 0.
[0093]
In the general formula (IV), R₂, R₃, R₄As a typical example of the alkyl group, alkenyl group, alkynyl group, aryl group or heterocyclic group represented by the general formula (III),₁And the same groups as described above. R₂, R₃Preferably, an alkyl group or an aryl group can be mentioned.₄Is preferably an alkyl group or an aryl group, more preferably an alkyl group, and most preferably an unsubstituted alkyl group.
[0094]
In the general formula (IV), L represents a divalent linking group, preferably an alkylene group or an arylene group, and n represents 0 or 1, and preferably 0.
[0095]
In the general formula (V), R₅As the unsubstituted alkyl group, unsubstituted alkenyl group and unsubstituted alkynyl group having 5 or more carbon atoms, which may be branched or linear, a hexyl group, octyl group, decyl group, dodecyl group , 1,1,3-trimethylbutyl group, oleyl group, cyclohexenyl group, adamantyl group and the like.
[0096]
R₆And R₇As representative examples of the alkyl group, alkenyl group, alkynyl group, aryl group and heterocyclic group represented by the formula: R in the general formula (III)₁And the same groups as described above. R₆Is preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom. R₇Is preferably an alkyl group or an aryl group.
[0097]
J₁Is preferably -NR₁₁-. R₁₁Is R in the general formula (III)₁Is synonymous with
[0098]
In the general formula (V), L represents a divalent linking group, and is preferably an alkylene group or an arylene group.
[0099]
In the general formula (V), n represents 0 or 1, and preferably 0.
In the general formula (VI), R₈, R₉And R₁₀As the alkyl group, alkenyl group, alkynyl group, aryl group or heterocyclic group represented by the general formula (III),₁And the same groups as described above.
[0100]
In the general formula (VI), L represents a divalent linking group, and is preferably an alkylene group or an arylene group.
[0101]
In the general formula (VI), n represents 0 or 1, and preferably 1.
Hereinafter, typical examples of the cyan couplers represented by the general formulas (III) to (VI) are shown, but the present invention is not limited thereto.
[0102]
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[0103]
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[0104]
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[0105]
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[0106]
The cyan coupler according to the present invention is generally used in the silver halide emulsion layer in an amount of 1 × 10 5 per mole of silver halide.^-3~ 1 mol, preferably 1 × 10^-2~ 8 × 10^-1It can be used in the molar range.
[0107]
The cyan coupler according to the present invention is preferably used together with a compound having a relative dielectric constant of 6 or more from the viewpoint of hue.
[0108]
In order to adjust the spectral absorption characteristics of the magenta image, cyan image, and yellow image according to the present invention, it is preferable to add a compound having a color tone adjusting effect.
[0109]
One of the features of the invention according to claim 2 is that the yellow image forming unit contains a phosphoric acid ester or a phosphine oxide compound together with the coupler represented by the general formula (I), and preferably has the following general formula ( IX).
[0110]
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[0111]
In the general formula (IX), R₂₁, R₂₂And R₂₃Represents an aliphatic group or an aromatic group, and p, q and r each represent 0 or 1.
[0112]
R₂₁, R₂₂And R₂₃Examples of the aliphatic group represented by are linear or branched alkyl, alkenyl, alkynyl or cycloalkyl groups having 1 to 30, preferably 1 to 20 carbon atoms. Specifically, for example, methyl, ethyl, propyl, butyl, hexyl, decyl, dodecyl, isopropyl, t-butyl, 2-ethylhexyl, allyl, 2-butenyl, 7-octenyl, propargyl, 2-butynyl, cyclopropyl, And groups such as cyclopentyl, cyclohexyl, cyclododecyl and the like. R₂₁, R₂₂And R₂₃Examples of the aromatic group represented by are those having 6 to 20 carbon atoms, and specific examples thereof include groups such as phenyl, naphthyl, and anthranyl. These R₂₁, R₂₂And R₂₃The aliphatic group or aromatic group represented by may be further substituted, and the substituent is not particularly limited, but typically, alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, Examples of each group include alkenyl, cycloalkyl and the like. Siloxy, acyloxy, sulfonyloxy, carbamoyloxy, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, heterocyclic thio, thioureido, carboxyl, Dorokishiru, mercapto, nitro, each group such as sulfo, and a spiro compound residue, bridged hydrocarbon compound residue and the like are also mentioned.
[0113]
Hereinafter, typical specific examples of the compound represented by Formula (IX) will be shown, but the present invention is not limited thereto.
[0114]
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[0115]
One of the features of the invention according to claim 2 is that the magenta image forming unit contains the compound represented by the general formula (II), an alcohol compound having 10 or more carbon atoms, and a phosphate or phosphine oxide compound. It is in. As the alcohol compound having 10 or more carbon atoms, a compound represented by the following formula (X) can be preferably mentioned.
[0116]
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[0117]
In the general formula (X), R₃₁Are a) an unsubstituted alkyl group or an unsubstituted alkenyl group, b) a substituted alkyl group or a substituted alkenyl group (provided that each of the substituted groups is an aryl group, an alkenyl group, a halogen atom, an alkoxycarbonyl group) And at least one substituent selected from acyloxy groups), c) an unsubstituted aryl group, and d) an aryl group containing at least one substituent selected from an alkyl group, an alkoxy group, an alkoxycarbonyl group, and an acyloxy group; Selected from the group consisting of₃₂And R₃₃Is independently a hydrogen atom or R₃₁Selected from the group of groups represented by₃₁, R₃₂And R₃₃Is 10 or more, preferably 10 to 30.
[0118]
In the general formula (X), preferably, R₃₁Is a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkenyl group. More preferably, R₃₂And R₃₃At least one is a hydrogen atom, or R₃₂And R₃₃Is a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkenyl group. For example, R₃₁Is a linear or branched alkyl group;₃₂And R₃₃Takes a hydrogen atom, the general formula (X) is_mH_2m-1—OH (where m is preferably an integer of 10 to about 30). Also, R₃₁And R₃₂Is independently linear or branched alkyl;₃₃Takes a hydrogen atom, the general formula (X) is_nH_2n-1CH (C_mH_2m-1) OH, where n + m preferably ranges from 9 to about 29. Also, R₃₁Is a linear or branched alkenyl group;₃₂And R₃₃Takes a hydrogen atom, the general formula (X) represents (C_mH_2m-1) CH = CH (CH₂)_nCH₂—OH (where m + n is preferably an integer from 7 to about 27). Also, R₃₁Is an aryl-substituted alkyl group;₃₂And R₃₃Takes a hydrogen atom, the general formula (X) represents (C₂H₄) C_nH_2n—OH, where n is preferably an integer from 4 to about 24. Particularly preferably, R₃₁Is a substituted or unsubstituted aryl group;₃₂And R₃₃At least one of them takes a hydrogen atom.
[0119]
Hereinafter, typical specific examples of the alcohol compound having 10 or more carbon atoms represented by the general formula (X) are shown, but the present invention is not limited thereto.
[0120]
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[0121]
Preferred examples of the phosphate or phosphine oxide compound used in combination with the alcohol compound having 10 or more carbon atoms include the compound represented by the general formula (IX).
[0122]
The total amount of the alcohol compound having 10 or more carbon atoms and the phosphoric acid ester or phosphine oxide compound and the addition ratio of the magenta coupler can be used in a mass ratio of 0.1: 1 to 10: 1, The ratio of the alcohol compound having 10 or more carbon atoms to the phosphate compound or phosphine oxide compound can be selected from any mixing ratio of 1:99 to 99: 1.
[0123]
One feature of the invention according to claim 2 is that the cyan image forming unit contains at least one compound represented by the general formula (III) and a high boiling organic solvent having a relative dielectric constant of 6 or more. It is in. It is thought to be due to the relationship with the structure of the coupler. However, when a compound having a small relative dielectric constant is used, there is a disadvantage that a dye having a hue suitable for a cyan image is hardly obtained. The high-boiling organic solvent as used herein refers to a solvent having a boiling point of about 175 ° C. or more at normal pressure, remaining in the light-sensitive material and exhibiting various functions, and may be a single compound, It may be a mixture. In the case of a mixture, it is necessary that the dielectric constant of the mixture is 6 or more. As expected from the high relative permittivity, the polar structure (carboxylate, carboxylic amide, phosphate, phosphate amide, phosphonate, phosphonate, phosphinate, phosphinate, phosphoryl) , A hydroxyl group bonded to a carbon atom, a halogen atom bonded to a carbon atom, an oxygen atom bonded to a carbon atom at both ends, or a nitrogen atom bonded to three carbon atoms).
[0124]
The high-boiling organic solvent used in the present invention may be liquid or solid at room temperature and pressure, or may be a low molecular weight compound or a high molecular weight (or polymer) compound. .
[0125]
In the present invention, as the definition of the high-boiling organic solvent, compounds known to those skilled in the art to have the following properties as main functions are excluded. For example, an anti-fading agent (radical scavenger, energy quencher, etc.), an ultraviolet absorber, an oxidized developing agent scavenger (a color mixing inhibitor, a high contrast agent, a competitive compound), a developing agent scavenger, a color increase preventing agent for an image after processing, Stain inhibitors due to light, heat and humidity, and bleach stain inhibitors are not included in the category of high-boiling organic solvents.
[0126]
The relative permittivity referred to in the present invention is a relative permittivity with respect to a vacuum, and can be easily measured by a method such as a modifier bridge method. In the present invention, a value measured at a measurement temperature of 25 ° C. and a measurement frequency of 10 kHz was used. When a high boiling organic solvent is used as a mixture, the relative permittivity of the mixture of the high boiling organic solvent is measured. If the high-boiling organic solvent is solid at room temperature, the relative dielectric constant can be heated and melted and measured as a supercooled liquid, or mixed by changing the mixing ratio with a high-boiling organic solvent with a known relative dielectric constant. The dielectric constant can be measured and determined as an extrapolated value of a plot of mass fraction versus relative dielectric constant.
[0127]
Specific compounds and measured values are described in detail in JP-A-2001-117205 and the like.
[0128]
Hereinafter, examples of the high boiling point organic solvent having a relative dielectric constant of 6 or more will be described, but the present invention is not limited thereto.
[0129]
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[0130]
In the light-sensitive material according to the present invention, the silver halide emulsion layer is laminated and coated on a support, but the order from the support may be any order. In addition, an intermediate layer, a filter layer, a protective layer, and the like can be provided as necessary.
[0131]
An anti-fading agent can be used in combination with each of the magenta, cyan, and yellow couplers to prevent fading of the formed dye image due to light, heat, humidity, and the like. Preferred compounds include phenyl ether compounds represented by the general formulas I and II described on page 3 of JP-A-2-66541, phenolic compounds represented by the general formula IIIB described in JP-A-3-174150, and Amine compounds represented by the general formula A described in JP 90445 and metal complexes represented by the general formulas XII, XIII, XIV and XV described in JP-A-62-182741 are particularly preferred for magenta dyes. Further, the compound represented by the general formula I 'described in JP-A-1-19649 and the compound represented by the general formula II described in JP-A-5-11417 are particularly preferable for yellow and cyan dyes.
[0132]
When an oil-in-water emulsion dispersion method is used to add a stain inhibitor or other organic compound used in the silver halide light-sensitive material according to the present invention, a water-insoluble high-boiling organic compound having a boiling point of 150 ° C or higher is usually used. If necessary, a low-boiling point and / or water-soluble organic solvent is used in combination in the solvent, and the mixture is dissolved and emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. As a dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser or the like can be used. After or simultaneously with the dispersion, a step of removing the low boiling organic solvent may be added. Examples of the high boiling point organic solvent that can be used for dissolving and dispersing the stain inhibitor include phosphate esters such as tricresyl phosphate and trioctyl phosphate; phosphine oxides such as trioctyl phosphine oxide; Higher alcohol compounds represented by (ai) to (ax) described on page 5 of 4-265975 are preferably used. Further, the high boiling point organic solvent preferably has a dielectric constant of 3.5 to 7.0. Two or more high boiling organic solvents can be used in combination.
[0133]
Preferred compounds as a surfactant used for dispersing a photographic additive used in the photosensitive material according to the present invention and adjusting a surface tension at the time of coating include a hydrophobic group having 8 to 30 carbon atoms in one molecule and a sulfone. Those containing an acid group or a salt thereof are mentioned. Specific examples include A-1 to A-11 described in JP-A-64-26854. Also, a surfactant in which a fluorine atom is substituted for an alkyl group is preferably used. These dispersions are usually added to a coating solution containing a silver halide emulsion, but it is better that the time from dispersion to the addition to the coating solution and the time from the addition to the coating solution to the coating are shorter. Each is preferably within 10 hours, more preferably within 3 hours, particularly preferably within 20 minutes.
[0134]
In the silver halide light-sensitive material according to the present invention, a compound that reacts with an oxidized developing agent is added to a layer between the light-sensitive layers to prevent color turbidity, or to a silver halide emulsion layer. It is preferable to improve the fog by adding it. The compound for this purpose is preferably a hydroquinone derivative, and more preferably a dialkylhydroquinone such as 2,5-di-t-octylhydroquinone. Particularly preferred compounds are those represented by the general formula II described in JP-A-4-133056, and include compounds II-1 to II-14 described on pages 13 to 14 and compound 1 described on page 17.
[0135]
It is preferable to add an ultraviolet absorber to the light-sensitive material according to the present invention to prevent static fog or improve the light fastness of the dye image. Preferred ultraviolet absorbers include benzotriazoles. Particularly preferred compounds are those represented by the general formula III-3 described in JP-A-1-250944 and those represented by the general formula III described in JP-A-64-66646. Compounds described in JP-A-63-187240, compounds represented by the general formula I described in JP-A-4-1633, compounds represented by the general formula (I) described in JP-A-5-165144, The compound shown by (II) is mentioned.
[0136]
It is preferable that the light-sensitive material according to the present invention contains an oil-soluble dye or pigment because whiteness is improved. Typical specific examples of the oil-soluble dyes include compounds 1 to 27 described in JP-A-2-842, pages 8-9.
[0137]
In the silver halide light-sensitive material according to the present invention, it is advantageous to use gelatin as a binder, but if necessary, other gelatin, for example, a gelatin derivative, a graft polymer of gelatin and another polymer, and a gelatin other than gelatin. A hydrophilic colloid such as a protein, a sugar derivative, a cellulose derivative, or a synthetic hydrophilic polymer such as a homopolymer or a copolymer can also be used.
[0138]
As the hardener of these binders, it is preferable to use a vinyl sulfone hardener or a chlorotriazine hardener alone or in combination. It is preferable to use the compounds described in JP-A-61-249054 and JP-A-61-245153. Further, it is preferable to add a preservative and an antifungal agent as described in JP-A-3-157646 to the colloid layer in order to prevent the growth of mold and bacteria which adversely affect the photographic performance and image storability. In order to improve the physical properties of the photosensitive material or the surface of the photosensitive material after processing, it is preferable to add a slipping agent or a matting agent described in JP-A-6-118543 or JP-A-2-73250 to the protective layer.
[0139]
As the support used in the photosensitive material according to the present invention, any material may be used, and paper coated with polyethylene or polyethylene terephthalate, a paper support made of natural pulp or synthetic pulp, a vinyl chloride sheet, a white pigment, Polypropylene, polyethylene terephthalate support, baryta paper and the like which may be contained can be used. Among them, a support having a water-resistant resin coating layer on both sides of the base paper is preferable. As the water-resistant resin, polyethylene, polyethylene terephthalate or a copolymer thereof is preferable.
[0140]
A support having a water-resistant resin coating layer on the surface of paper is usually 50 to 300 g / m2.²Is used. For the purpose of obtaining a proof image, in order to bring the feeling of handling closer to printing paper, 130 g / m2 is used.²The following base papers are preferably used, and 70 to 120 g / m²Base paper is preferably used. The support used in the present invention can be preferably used regardless of whether it has random irregularities or is smooth.
[0141]
As the white pigment used for the support, an inorganic and / or organic white pigment can be used, and an inorganic white pigment is preferably used. For example, sulfates of alkaline earth metals such as barium sulfate, carbonates of alkaline earth metals such as calcium carbonate, finely divided silica, silicas such as synthetic silicate, calcium silicate, alumina, alumina hydrate, Examples include titanium oxide, zinc oxide, talc, and clay. The white pigment is preferably barium sulfate or titanium oxide. The amount of the white pigment contained in the water-resistant resin layer on the surface of the support is preferably 13% by mass or more, and more preferably 15% by mass, in order to improve sharpness.
[0142]
The degree of dispersion of the white pigment in the water-resistant resin layer of the paper support according to the present invention can be measured by the method described in JP-A-2-28640. When measured by this method, the degree of dispersion of the white pigment is preferably 0.20 or less, more preferably 0.15 or less, as the variation coefficient described in the above-mentioned publication.
[0143]
The resin layer of the paper support having a water-resistant resin layer on both sides used in the present invention may be a single layer or a plurality of layers. It is preferable to form a plurality of layers and to include a white pigment at a high concentration in contact with the emulsion layer, because sharpness is greatly improved and a proofing image is formed.
[0144]
Further, it is more preferable that the value of the center plane average roughness (SRa) of the support surface be 0.15 μm or less, and more preferably 0.12 μm or less, since the effect of good gloss can be obtained for photographic use. In the use of the proof, those having a thickness of 0.8 to 2 μm are preferably used from the viewpoint of approximation to printed matter.
[0145]
In the light-sensitive material according to the present invention, the surface of the support is subjected to corona discharge, ultraviolet irradiation, flame treatment, etc., if necessary, and then directly or to an undercoat layer (adhesion, antistatic property, dimensional stability of the support surface). , Abrasion resistance, hardness, antihalation properties, frictional properties and / or other properties.
[0146]
When coating a light-sensitive material using a silver halide emulsion, a thickener may be used to improve coatability. Extrusion coating and curtain coating, in which two or more layers can be applied simultaneously, are particularly useful as a coating method.
[0147]
As the exposure light source of the exposure apparatus used in the present invention, any known light source can be preferably used, but a laser or a light emitting diode (hereinafter, referred to as LED) is more preferably used.
[0148]
As a laser, a semiconductor laser (hereinafter, referred to as LD) is preferably used because it is compact and has a long light source life. In addition, LDs are used for applications such as optical pickups for DVDs and music CDs, barcode scanners for POS systems, and for applications such as optical communication, and have the advantage of being inexpensive and having a relatively high output. have. Specific examples of LD include aluminum gallium indium arsenide (650 nm), indium gallium phosphorus (リ ン 700 nm), gallium arsenic phosphorus (610 to 900 nm), and gallium aluminum arsenide (760 to 850 nm). ) And the like. Recently, a laser emitting blue light has been developed, but at present, it is advantageous to use an LD as a light source having a longer wavelength than 610 nm.
[0149]
As a laser light source having an SHG element, light emitted from an LD or YAG laser is converted into half-wavelength light by the SHG element and emitted. Since a visible light is obtained, there is no green light source. Used as a light source in the blue region. As an example of this type of light source, there is a combination of a YAG laser and an SHG element (532 nm).
[0150]
Examples of the gas laser include a helium-cadmium laser (about 442 nm), an argon ion laser (about 514 nm), and a helium neon laser (about 544 nm and 633 nm).
[0151]
As an LED, an LED having a composition similar to that of an LD is known, but various LEDs from blue to infrared have been put to practical use.
[0152]
As an exposure light source used in the present invention, each laser may be used alone, or a combination thereof may be used as a multi-beam. In the case of an LD, for example, by arranging ten LDs, a beam composed of ten light beams can be obtained. On the other hand, in the case of a helium neon laser, the light emitted from the laser is split into, for example, ten light beams by a beam separator.
[0153]
In the case of an LD or LED, the intensity of the exposure light source can be directly modulated by changing the value of the current flowing through each element. In the case of an LD, the intensity may be changed using an element such as an AOM (acoustic optical modulator). In the case of a gas laser, a device such as an AOM or an EOM (electro-optic modulator) is generally used.
[0154]
When an LED is used as a light source, a method may be used in which the same pixel is repeatedly exposed by a plurality of elements as long as the amount of light is weak.
[0155]
Organic light emitting elements may be used as light sources instead of these, and these are described in, for example, JP-A-2000-258846.
[0156]
One of the features of the present invention is that the resolution of the exposure apparatus is 1000 dpi or more, which means that the minimum beam diameter of exposure is 25.4 μm or less. The term “dpi” in the present invention indicates the number of dots per 2.54 cm.
[0157]
Where the resolution of the exposure device is small, the hue fluctuation before and after the continuous development process (running process) due to the change in the halftone dot percentage of the secondary and tertiary colors is small, but it is difficult to form a clear area-modulated image. Not suitable for use in the present invention. Further, although smaller than 6 μm is preferable in terms of image quality, it is difficult to adjust the color tone and the processing speed is reduced.
[0158]
In the present invention, the term area-modulated or area-modulated image is used, but this does not mean that the shade on the image is represented by the shade of the color of each pixel, but by the size of the area of the part that has developed to a particular density. It means to express and may be considered as synonymous with halftone dot. Also, the terms density modulation and density modulation image are used, which means that the density of the color of a pixel is represented by changing the density, and is synonymous with a continuous tone image in a broad sense.
[0159]
One of the features of the present invention is that a halftone dot is formed as an aggregate of pixels (hereinafter, also referred to as dots) whose density can be changed. In a system that forms an area gradation image based on digital data, it is possible to divide a halftone dot into smaller pixels, and to reproduce the halftone dot as an aggregate by exposing this pixel with an appropriate exposure amount. . As a simple example, if one halftone dot is composed of 100 pixels, halftone dots are formed by exposing 50 pixels so that halftone% can be developed. You can do it. In the case of normal area gradation exposure, the purpose can be achieved by developing Y, M, C, and black. However, if the density can be changed, overprint colors and spot colors can be reproduced, and the usefulness of the proof image becomes extremely high.
[0160]
One of the features of the present invention is to form an image using the relationship between the exposure amount of the silver halide photosensitive material and the amount corresponding to the amount of the image dye and the relationship between the pixel color and the amount corresponding to the amount of the image dye. The purpose is to find the necessary exposure. Any amount corresponding to the amount of image dye can be preferably used as long as it corresponds to the amount of image dye on a one-to-one basis. In extreme cases, the amount of the dye itself may be used. As the amount corresponding to the amount of the image dye, a density (optical density) often used in the field of printing, coordinates in the CIELAB color space, or the like can be used. For example, in the case of Y dye, B density, b in CIELAB color space^*Etc. are appropriate. These may be used in an appropriate combination amount. For example, a metric chroma in the CIELAB color space can be used for a C dye. One of the suitable ones is an analytical concentration.
[0161]
Analytical density is a concept of density that is often used in the field of photography. When Y, M, and C dyes are formed in an arbitrary amount, and when only the Y dye is formed in the same amount, the B density is analyzed analytically. The G density when only the M dye is colored in the same amount is called the analytical G density, and the R density when only the C dye is colored in the same amount is called the analytical R density. Analytical concentration is a conceptual quantity, but can also be determined by calculation. Regarding the analytical concentration, H. James, Ed., The Theory of The Photographic Process, Macmillan, New York, p. 524-529 (1977), which can be determined with reference to this. A useful embodiment of the present invention is a system using a silver halide photosensitive material having a reflective support. In this case, it is preferable that the analytical density is also represented as the reflection density. From the point of handling of numerical values, a numerical value converted from the original analytical density may be used, and it is preferable to multiply the analytical density by 100 and convert it to an integer, since it is easier to handle and it is preferable.
[0162]
In the present invention, the relationship between the exposure amount of the silver halide light-sensitive material and the amount corresponding to the amount of the image dye (here, the analytical density) is described. The light-sensitive material characteristic TBL in FIG. 2 is an example of this. For the relationship between exposure and density, create a color patch in all combinations where the exposure is changed in arbitrary increments, and use this measurement as a database to refer to this database when given any color. By doing so, the exposure amount of each layer can be obtained. However, in this case, in order to improve the accuracy, it is necessary to perform an enormous amount of measurements and create a database. On the other hand, in the method of expressing by the analytical density, by determining the relationship between the exposure amount of each of the Y, M, and C layers and the color density, the required exposure amount can be accurately obtained with a small amount of data. There is an advantage that it is easy to respond to a change in the color stage of the photosensitive material at the design stage or the like. The fact that the reproduced color of the secondary color can be easily reproduced to a desired color enhances the value of the color image forming method of the present invention in combination with the stable reproduction of the hue of the color whose dot percentage has changed. . The analytical density here does not need to particularly define the spectral conditions and the like, and it suffices if the data that defines the desired density and the density that describes the characteristics of the image forming material have the same definition. The status T generally used in the field of printing may be used, and in order to improve the accuracy, it is preferable to use the status A from the relationship between the spectral density distribution and the spectral product.
[0163]
In the present invention, the relationship between the color of the pixel and the amount corresponding to the amount of the image dye (in this case, the analytical density) is described. The density TBL of the photosensitive layer for each color in FIG. 2 is an example.
[0164]
Next, a processing operation for editing image data into exposure data will be described with reference to FIGS. First, the number (counter: i) of a pixel from which data is to be read is set to 1, and Y, M, C, K, and special color image data of pixel 1 are read. Next, the color of the pixel is determined by combining which color is being developed. This is accomplished by referencing a table. For example, in pixel 1, since only Y is colored, the color of the pixel is determined to be Y in the column where only Y in the color discrimination TBL is 1. In the pixel 3, since Y and M are colored, the color of the pixel is R. Similarly, the color of the pixel 4 is also K because only K is colored, and the color of the pixel 5 is K + M, which is an overprint color, since the pixel 5 is colored by K and M. Image data for each pixel is created by such conversion. Next, an exposure amount to be applied to each of the Y, M, and C image forming layers is read from a table to create this color, and the exposure amount to be applied to each layer is arranged for each pixel as image data. Transfer to
[0165]
A specific flow of this operation will be described with an example in which the characteristics of a silver halide photosensitive material are represented by an analytical density (integrated by multiplying by 100). The analytical density of each layer is determined by referring to the density TBL of each photosensitive layer for each color from the color of the pixel. In this example, it can be seen that pixel 1 develops only Y at level 1 (analytical density 110). Based on this, it can be seen from the photosensitive material characteristics TBL that the exposure amount of Y is at the level (n-4). Similarly, the exposure level for M and C can be determined. Exposure data is created for each pixel.
[0166]
When the processing for each pixel is completed, the counter is incremented by 1 and the processing for the next pixel is performed. Hereinafter, this process is repeated to create exposure amount data for each pixel. The timing of data transfer to the image output means may be performed in pixel units, at the time when data processing required for one main scan is completed, or at the time when all data processing is completed. Good. The image output means converts this data into a signal for controlling the device as necessary, and performs exposure.
[0167]
The image output means converts the exposure amount data into a drive signal for an exposure device as necessary based on the exposure amount data, and performs exposure. The process of converting the exposure device into a drive signal may be included in the image processing means. In the image output means, a data buffer may be provided as needed to adjust the timing of exposure.
[0168]
FIG. 2 shows the data structure assumed at this time. It is assumed that the image data has only data on whether or not each color is colored in the order of pixels. The color of the pixel is determined by referring to the table from the pattern of the combination of Y, M, C, K and the presence / absence of the spot color. Next, the exposure amount to be given to each layer is determined with reference to the table of the pixel colors and the exposure amounts of the Y, M, and C image forming layers. Separating the place where the color of the pixel is determined and the place where the amount of exposure of each image forming layer is determined from the color of the pixel is such that, for example, R can be set independently of simple addition of Y and M of a single color. It may be expressed by simple addition according to the required specification. By being able to set independently, an image closer to printing can be obtained, and an image in the case of printing in two colors of green and red using two image data can be obtained. It can be used for checking, and a highly useful system can be realized.
[0169]
Although the above description has described a case where the number of exposure devices is one, if the number of exposure devices is ten in the sub-scanning direction, pixels 1 to 10 represent pixels arranged in the sub-scanning direction, Data that is shifted by one pixel in the main scanning direction may be read as being represented by pixels 11 to 20.
[0170]
In general, where the density is low, even a slight change in density tends to be noticeable as a color change. Although the system capable of changing the density of halftone dots has various advantages as described above, it is possible to use an area where the fluctuation is conspicuous, and it is desired to further stabilize the color. It is rare. The effect of the present invention that the hue fluctuation before and after the continuous development processing due to the change of the halftone dot percentage of the secondary color is small irrespective of the storage state of the silver halide photosensitive material is the effect of the color required by the system capable of changing the halftone dot density. It is useful as a means to increase stability.
[0171]
One of the features of the invention according to claim 3 is that an image in which a specific pattern is superimposed on an original image is output as a density-modulated image. For example, a pattern that separates pixels in a grid shape is overwritten on the original image. By outputting an image as a density-modulated image with a uniform density for each pixel, it is possible to describe an image corresponding to a halftone dot difference with a small change in hue.
[0172]
To draw an image with such light, it is necessary for the light beam to scan over the silver halide photosensitive material.However, the photosensitive material is wound around a cylindrical drum and rotated at high speed in a direction perpendicular to the rotation direction. A cylindrical outer surface scanning method in which a light beam is moved may be used, and a cylindrical inner surface scanning method in which a silver halide photosensitive material is brought into close contact with a cylindrical recess and exposed is preferably used. A plane scanning method may be adopted in which the polyhedral mirror is rotated at a high speed and the silver halide light-sensitive material conveyed thereby is exposed by moving a light beam at right angles to the conveying direction. In order to obtain a high quality and large image, a cylindrical outer surface scanning method is more preferably used.
[0173]
In order to perform exposure by the cylindrical outer surface scanning method, the silver halide photosensitive material must be accurately brought into close contact with a cylindrical drum. In order for this to be performed properly, it is necessary that the wafer be transported while being accurately aligned. The silver halide light-sensitive material used in the present invention is preferably used when the surface on the side to be exposed is rolled outward, so that the alignment can be more accurately performed. From the same viewpoint, the support used for the silver halide light-sensitive material used in the present invention has appropriate rigidity, and preferably has a Taber rigidity of 0.8 to 4.0.
[0174]
The drum diameter can be arbitrarily set in accordance with the size of the silver halide photosensitive material to be exposed. The number of rotations of the drum can be arbitrarily set, but an appropriate number of rotations can be selected according to the beam diameter of the laser beam, the energy intensity, the writing pattern, the sensitivity of the photosensitive material, and the like. From the viewpoint of productivity, it is preferable that scanning exposure can be performed at higher rotation speed, but specifically, 200 to 3000 rotations per minute is preferably used.
[0175]
The method of fixing the silver halide photosensitive material to the drum may be fixed by mechanical means, or a large number of fine holes that can be suctioned on the drum surface are provided according to the size of the photosensitive material, and the photosensitive material is fixed. It can also be brought into close contact by suction. It is important to make the photosensitive material as close as possible to the drum in order to prevent troubles such as uneven images.
[0176]
One of the features of the invention according to claim 5 is that the exposure apparatus has a printing condition profile that associates the digital image information with the device-independent image data, and the device-independent image data and the exposure digital image data. And a color conversion unit that converts the digital image information into the exposure digital image data based on an exposure condition profile that associates This is known as a so-called color management system (CMS), but in order to maximize the use of the color gamut, there are restrictions such as restricting the solid portion of the CMS so that other colors are not mixed. However, the color tone may be adjusted by causing other solid dyes to be color-modulated in a solid area and having a density lower than a specific density to develop a color.
[0177]
Known compounds can be used as the aromatic primary amine developing agent used in the present invention. The following compounds can be mentioned as examples of these compounds.
[0178]
CD-1: N, N-diethyl-p-phenylenediamine
CD-2: 2-amino-5-diethylaminotoluene
CD-3: 2-amino-5- (N-ethyl-N-laurylamino) toluene
CD-4: 4- (N-ethyl-N- (β-hydroxyethyl) amino) aniline
CD-5: 2-methyl-4- (N-ethyl-N- (β-hydroxyethyl) amino) aniline
CD-6: 4-amino-3-methyl-N-ethyl-N- (β- (methanesulfonamido) ethyl) -aniline
CD-7: N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide
CD-8: N, N-dimethyl-p-phenylenediamine
CD-9: 4-amino-3-methyl-N-ethyl-N-methoxyethylaniline
CD-10: 4-amino-3-methyl-N-ethyl-N- (β-ethoxyethyl) aniline
CD-11: 4-amino-3-methyl-N-ethyl-N- (γ-hydroxypropyl) aniline
In the invention according to claim 6, 4-amino-3-methyl-N-ethyl-N- (β- (methanesulfonamido) ethyl) aniline, which is Exemplified Compound CD-6, is used as the color developing agent. preferable. Use of this developing agent enables more stable hue reproduction.
[0179]
In the present invention, the above-described color developer containing a color developing agent can be used in an arbitrary pH range. However, from the viewpoint of rapid processing, the pH is preferably 9.5 to 13.0, more preferably pH 9.8 to 9.8. Used in the range of 12.0.
[0180]
The processing temperature of the color developing solution according to the present invention is preferably 35 ° C. or more and 70 ° C. or less. The higher the temperature, the shorter the processing time is possible, which is preferable. However, from the viewpoint of the stability of the processing solution, the higher the temperature, the more preferable.
[0181]
Conventionally, the color development time is generally about 3 minutes and 30 seconds, but in the present invention, it is preferably within 40 seconds, and more preferably within 25 seconds.
[0182]
In the color developing solution, in addition to the above-described color developing agent, a known developing solution component compound can be added. For example, a development inhibitor such as an alkali agent having a pH buffering action, chloride ions, and benzotriazoles can be used. , Preservatives, chelating agents and the like are used.
[0183]
The silver halide light-sensitive material according to the present invention is subjected to bleaching and fixing after color development. The bleaching process may be performed simultaneously with the fixing process. After the fixing process, a washing process is usually performed. Further, as an alternative to the water washing treatment, a stabilization treatment may be performed. The developing apparatus used for developing the silver halide photosensitive material according to the present invention is a roller transport type in which the photosensitive material is transported across rollers arranged in a processing tank, and the photosensitive material is applied to a belt. An endless belt system that transports the material in a fixed manner may be used.However, a processing tank is formed in a slit shape, and a processing liquid is supplied to this processing tank and the photosensitive material is transported. A method, a web method by contact with a carrier impregnated with a treatment liquid, a method using a viscous treatment liquid, and the like can also be used. In the case of processing in large quantities, it is preferable to carry out running processing using an automatic developing machine. At this time, it is preferable that the replenisher amount of each processing solution is smaller, and the most preferable processing form from environmental suitability and the like is tablet processing as a replenishment method. And the method described in JP-A-94-16935 is most preferable.
[0184]
【Example】
Hereinafter, the present invention will be described in detail with reference to examples, but embodiments of the present invention are not limited thereto.
[0185]
Example 1
A polyethylene-laminated paper reflective support having a mass per square meter of 115 g, in which high-density polyethylene is laminated on one side and fused polyethylene containing anatase-type titanium oxide dispersed at a content of 15% by mass on the other side is 115 g per square meter. (Stiffness = 3.5, PY value = 2.7 μm), each layer having the composition shown in Table 1 was applied on the polyethylene layer containing titanium oxide, and gelatin 6.00 g / m 2 on the back side.², Silica matting agent 0.65 g / m²A multilayer silver halide photosensitive material sample 101 coated with was prepared.
[0186]
Each coupler described in Table 1 was dissolved in a high boiling point solvent and ethyl acetate, emulsified and dispersed in a gelatin solution containing a surfactant using an ultrasonic disperser, and added as a dispersion. In addition, (SU-1) was used as a surfactant. (H-1) and (H-2) were added as hardeners. Surfactants (SU-2) and (SU-3) were added as coating aids to adjust the surface tension. The total amount of (F-1) was 0.04 g / m in each layer.²Was added so that
[0187]
[Table 1]

[0188]
SU-1: sodium tri-i-propylnaphthalenesulfonate
SU-2: di (2-ethylhexyl) sulfosuccinate sodium salt
SU-3: sulfosuccinate di (2,2,3,3,4,4,5,5-octafluoropentyl) sodium salt
H-1: tetrakis (vinylsulfonylmethyl) methane
H-2: 2,4-dichloro-6-hydroxy-s-triazine sodium
HQ-1: 2,5-di-t-octylhydroquinone
HQ-2: 2,5-di ((1,1-dimethyl-4-hexyloxycarbonyl) butyl) hydroquinone
HQ-3: a mixture of 2,5-di-sec-dodecylhydroquinone, 2,5-di-sectetradecylhydroquinone, and 2-sec-dodecyl-5-sec-tetradecylhydroquinone at a mass ratio of 1: 1: 2.
SO-1: trioctylphosphine oxide
SO-2: di (i-decyl) phthalate
SO-3: Oleyl alcohol
SO-4: tricresyl phosphate
PVP: polyvinylpyrrolidone
[0189]
Embedded image

[0190]
Embedded image

[0191]
The method for preparing each silver halide emulsion used in the preparation of Sample 101 is described below. (Preparation of blue-sensitive silver halide emulsion)
To 1 liter of a 2% gelatin aqueous solution kept at 40 ° C., the following (Solution A) and (Solution B) were simultaneously added while controlling pAg = 7.3 and pH = 3.0, and further the following (Solution C) And (Solution D) were added simultaneously while controlling pAg = 8.0 and pH = 5.5. At this time, the pAg was controlled by the method described in JP-A-59-45437, and the pH was appropriately controlled using sulfuric acid or an aqueous sodium hydroxide solution.
[0192]
(A liquid)
3.42 g of sodium chloride
Potassium bromide 0.03g
200 ml with water
(B liquid)
Silver nitrate 10g
200 ml with water
(Liquid C)
Sodium chloride 102.7g
Potassium hexachloroiridate (IV) 4 × 10^-8Mole
Potassium hexacyanoferrate (II) 2 × 10^-5Mole
1.0 g of potassium bromide
600 ml with water
(D liquid)
Silver nitrate 300g
600 ml with water
After completion of the addition, desalting was carried out using a 5% aqueous solution of Demol N and 20% aqueous solution of magnesium sulfate manufactured by Kao Atlas Co., Ltd. EMP-101, a monodisperse cubic emulsion having a silver chloride content of 0.07 and a silver chloride content of 99.5 mol%, was obtained.
[0193]
The above-mentioned EMP-101 was optimally subjected to chemical sensitization at 60 ° C. using the following compounds to obtain a blue-sensitive silver halide emulsion Em-B101.
[0194]
Sodium thiosulfate 0.8mg / mol AgX
Chloroauric acid 0.5mg / mol AgX
Stabilizer: STAB-1 3 × 10^-4Mol / mol AgX
Stabilizer: STAB-2 3 × 10^-4Mol / mol AgX
Stabilizer: STAB-3 3 × 10^-4Mol / mol AgX
Sensitizing dye: BS-1 4 × 10^-4Mol / mol AgX
Sensitizing dye: BS-2 1 × 10^-4Mol / mol AgX
Potassium bromide 0.2 g / mol AgX
STAB-1: 1-phenyl-5-mercaptotetrazole
STAB-2: 1- (4-ethoxyphenyl) -5-mercaptotetrazole
STAB-3: 1- (3-acetamidophenyl) -5-mercaptotetrazole
Next, in the preparation of EMP-101, the average particle diameter was 0.64 μm in the same manner except that the addition time of (Solution A) and (Solution B) and the addition time of (Solution C) and (Solution D) were changed. Thus, EMP-102 as a monodisperse cubic emulsion having a coefficient of variation in particle size distribution of 0.07 and a silver chloride content of 99.5 mol% was obtained.
[0195]
Em-B101 was prepared in the same manner as in the preparation of Em-B101 except that EMP-102 was used instead of EMP-101, and a 1: 1 mixture of Em-B101 and Em-B102 was treated with a blue-sensitive silver halide. Used as emulsion.
[0196]
Embedded image

[0197]
(Preparation of green photosensitive silver halide emulsion)
In the preparation of EMP-101, the average particle diameter was 0.40 μm and the variation coefficient was 0 in the same manner except that the addition times of (Solution A) and (Solution B) and (Solution C) and (Solution D) were changed. 0.08 and a monodisperse cubic emulsion having a silver chloride content of 99.5% was prepared.
[0198]
The above-mentioned EMP-103 was optimally chemically sensitized at 55 ° C. using the following compounds to obtain Em-G101 as a green photosensitive silver halide emulsion.
[0199]
Sodium thiosulfate 1.5mg / mol AgX
Chloroauric acid 1.0mg / mol AgX
Stabilizer: STAB-1 3 × 10^-4Mol / mol AgX
Stabilizer: STAB-2 3 × 10^-4Mol / mol AgX
Stabilizer: STAB-3 3 × 10^-4Mol / mol AgX
Sensitizing dye: GS-1 2 × 10^-4Mol / mol AgX
Sensitizing dye: GS-2 2 × 10^-4Mol / mol AgX
Sodium chloride 0.5g / mol AgX
Next, in the preparation of EMP-103, the average particle diameter was adjusted in the same manner except that the addition time of (Solution A) and (Solution B) and the addition time of (Solution C) and (Solution D) were changed. EMP-104, a monodisperse cubic emulsion having a particle size of 50 μm, a coefficient of variation of 0.08 and a silver chloride content of 99.5%, was obtained.
[0200]
Em-G102 was prepared in the same manner as in the preparation of Em-G101 except that EMP-104 was used instead of EMP-103, and a 1: 1 mixture of Em-G101 and Em-G102 was subjected to green photosensitive halogenation. Used as silver emulsion.
[0201]
Embedded image

[0202]
(Preparation of red-sensitive silver halide emulsion)
The above-prepared EMP-103 was optimally subjected to chemical sensitization at 60 ° C. using the following compounds to obtain Em-R101 as a red-sensitive silver halide emulsion.
[0203]
Sodium thiosulfate 1.8mg / mol AgX
Chloroauric acid 2.0mg / mol AgX
Stabilizer: STAB-1 2 × 10^-4Mol / mol AgX
Stabilizer: STAB-2 2 × 10^-4Mol / mol AgX
Stabilizer: STAB-3 2 × 10^-4Mol / mol AgX
Stabilizer: STAB-4 1 × 10^-4Mol / mol AgX
Sensitizing dye: RS-1 1 × 10^-4Mol / mol AgX
Sensitizing dye: RS-2 1 × 10^-4Mol / mol AgX
Supersensitizer: SS-1 2 × 10^-4Mol / mol AgX
STAB-4: p-toluenethiosulfonic acid
Next, the above-prepared EMP-103 was optimally chemically sensitized at 60 ° C. using the following compound to obtain Em-R102 which is a red-sensitive silver halide emulsion.
[0204]
Sodium thiosulfate 1.8mg / mol AgX
Chloroauric acid 2.0mg / mol AgX
Stabilizer: STAB-1 2 × 10^-4Mol / mol AgX
Stabilizer: STAB-2 2 × 10^-4Mol / mol AgX
Stabilizer: STAB-3 2 × 10^-4Mol / mol AgX
Stabilizer: STAB-4 1 × 10^-4Mol / mol AgX
Sensitizing dye: RS-1 2 × 10^-4Mol / mol AgX
Sensitizing dye: RS-2 2 × 10^-4Mol / mol AgX
Supersensitizer: SS-1 2 × 10^-4Mol / mol AgX
A 1: 1 mixture of Em-R101 and Em-R102 prepared above was used as a red-sensitive silver halide emulsion.
[0205]
Embedded image

[0206]
Next, in the preparation of Sample 101, the Y coupler (Y-1) used in the seventh layer was used in the third layer for equimolar amounts of (YC-3), (YC-14), and (YC-16). The C coupler (C-1) used in the fifth layer was equimolar to the (CC-2), (MC-7) and (MC-17), and the equimolar (CC). -5), (CC-7), (CC-9), and (CC-12) were prepared in the same manner as Samples 102 to 108 except that each of the combinations was replaced with a combination shown in Table 2.
[0207]
《Exposure and development processing》
(exposure)
Two copies of each of the above prepared samples were prepared, a part of which was frozen and stored, and another part was left under the condition of 50 ° C. and 40% RH for one week.^*, B^*) = (Blue: 26.5, -53.0), (green: -63.0, 22.0), (red: 65.5, 48.5) Exposure conditions were determined for each sample. The patches having halftone dot percentages of 40%, 50%, 60%, 70%, 80%, and 100% (solid) were exposed and developed under the following conditions.
[0208]
The following apparatus was prepared as an exposure apparatus.
Five LEDs of B as a light source were arranged in the main scanning direction, and the timing of the exposure was gradually delayed so that the same location could be exposed by the five LEDs. In addition, an exposure head was prepared in which 20 LEDs were arranged in the sub-scanning direction and exposure for 20 adjacent pixels could be performed at one time. For G and R, exposure heads were prepared by combining LEDs in the same manner. The diameter of each beam was about 10 μm, the beams were arranged at this interval, and the sub-scanning pitch was about 200 μm.
[0209]
(Development processing)
The exposed samples were subjected to the following development processing.
[0210]
The development processing was performed using both the processing using the color development starting solution and the solution that was subjected to the running processing until the total replenisher amount of the separately prepared replenisher became equal to the capacity of the color development tank.
[0211]
Treatment process Treatment temperature Time Replenishment amount
Color development 37.0 ± 0.3 ° C 120 seconds 200ml / m²
Bleaching and fixing 37.0 ± 0.5 ° C 90 seconds 150ml / m²
Stabilization 30-34 ° C 60 seconds 400ml / m²
Drying 60-80 ° C 30 seconds
<Color developer starting solution and replenisher>

Water was added to make the total volume 1 liter, the tank solution was adjusted to pH = 10.2, and the replenisher was adjusted to pH = 10.5.
[0212]
<Bleach-fixer solution and replenisher>
Diethylenetriaminepentaacetic acid ammonium ferric dihydrate 65g
3 g of diethylenetriaminepentaacetic acid
Ammonium thiosulfate (70% aqueous solution) 100ml
2-amino-5-mercapto-1,3,4-thiadiazole 2.0 g
Ammonium sulfite (40% aqueous solution) 27.5ml
Water was added to make the total volume 1 liter, and the pH was adjusted to 5.0 with potassium carbonate or glacial acetic acid.
[0213]
<Stabilizing solution tank solution and replenisher>
1.0 g of o-phenylphenol
5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g
2-methyl-4-isothiazolin-3-one 0.02 g
1.0 g of diethylene glycol
Optical brightener (Tinopearl SFP) 2.0g
1.8 g of 1-hydroxyethylidene-1,1-diphosphonic acid
0.5g zinc sulfate
Magnesium sulfate heptahydrate 0.2g
PVP (polyvinyl pyrrolidone) 1.0 g
Aqueous ammonia (25% ammonium hydroxide aqueous solution) 2.5 g
Nitrilotriacetic acid trisodium salt 1.5g
Water was added to make the total volume 1 liter, and the pH was adjusted to 7.5 with sulfuric acid or aqueous ammonia.
[0214]
《Image evaluation》
The sample obtained as described above was measured using a spectrophotometer CM-2022 manufactured by Minolta Co., using geometric conditions d-0 for illumination and light reception, and photometry using a xenon pulse light source. L^*a^*b^*Was determined. Next, a GOF value represented by the following equation 1 was obtained by approximating a straight line passing through the point (0, 0) by the least square method.
[0215]
(Equation 1)

[0216]
here,
α: coefficient obtained by the least squares method
ai: measured a^*The value of the
bi: measured b^*The value of the
bcal: b calculated by the following equation^*The value of the
bcal = α × ai
i: Integer of 1 to 6, halftone dot% indicates each measured value of 40%, 50%, 60%, 70%, 80%, and 100%
However, when evaluating blue, acal = α ′ × bi and a^*The GOF value was defined by estimating the value of.
[0217]
The difference (ΔGOF value) between the GOF value 1 obtained from the sample processed with the developing solution after the running process and the GOF value 2 obtained from the sample processed with the color development starting solution was obtained. The results are shown in Table 2.
[0218]
[Table 2]

[0219]
The GOF value is an amount corresponding to the standard deviation of the deviation from the isohue line, and can be said to be an amount representing the fluctuation of the hue as an average. Therefore, for blue and other colors, the a^*, B^*Was replaced.
[0220]
In the comparative sample 101, the GOF value 1 of the frozen preservation sample in the developing solution is 1.3 to 2.0, and the ΔGOF value is 1.0 to 1.8 even when the sample is processed with the processing solution after the running process. However, in the sample stored in an atmosphere of 50 ° C. and 40% RH, the GOF value 2 of the development starting solution was 1.5 to 1.9, while The ΔGOF value treated with the later treatment liquid showed a deterioration of 2.9 to 3.8. (The ΔGOF values are shown in Table 2.) In the sample of the present invention, even when the sample was stored in an atmosphere of 50 ° C. and 40% RH, the fluctuation was small even when the sample was treated with the processing solution after the running process. I understand. Looking at the data in detail, the sample using the coupler used in the present invention and the comparative coupler in the same photosensitive material gave relatively good results in the color in which the couplers used in the present invention were combined. Therefore, it is presumed that the influence of the factors relating to the coupler is large.
[0221]
Example 2
In Samples 101 to 108 prepared in Example 1, Samples 201 to 208 were prepared by replacing the high boiling solvents used for the yellow image forming unit and the magenta image forming unit with di- (2-ethylhexyl) phthalate having the same mass. did.
[0222]
Further, Samples 209 to 210 were prepared in the same manner as in Sample 208 except that the high boiling point solvent of the cyan image forming unit was changed to the exemplified compounds (HBS-1) and (HBS-2).
[0223]
Further, Sample 211 was prepared in the same manner as Sample 208 except that the high boiling point solvent of the yellow image forming unit was replaced with tri- (2-ethylhexyl) phosphate.
[0224]
Further, Sample 212 was prepared in the same manner as in Sample 208 except that the high boiling point solvent of the magenta image forming unit was replaced with an equal mixture of tri- (2-ethylhexyl) phosphate and oleyl alcohol. The relative dielectric constant of the mixture of the high boiling point solvents (SO-4) and (SO-5) was 6.10. These samples were evaluated in the same manner as in Example 1, and the obtained ΔGOF values are shown in Table 3.
[0225]
[Table 3]

[0226]
As is clear from Table 3, the effects of the present invention can be obtained in the same manner as in Example 1, even with a sample using di- (2-ethylhexyl) phthalate as the high boiling point solvent used in the yellow image forming unit and the magenta image forming unit. It can be seen that even in a sample stored in an atmosphere of 50 ° C. and 40% RH, the difference in hue between the developing solution and the developing solution after the running process is small. However, when Tables 2 and 3 are compared, it can be seen that the effect of the sample using trioctyl phosphine oxide (SO-1) or tri- (2-ethylhexyl) phosphate in the yellow image forming unit is large. Table 3 also shows that the magenta image forming unit used in combination with oleyl alcohol and trioctylphosphine oxide (SO-1) or tri (2-ethylhexyl) phosphate, and the cyan image forming unit used (HBS-1) and (HBS-2). ), The effect was found to be large.
[0227]
Example 3
The patch densities of the red, green, and blue halftone dot percentages of the sample 101 formed in Example 1 were 40%, 50%, 60%, 70%, 80%, and 100%, and the patches corresponded to the densities. Image data prepared by editing image data, natural images, and portrait images were prepared.
[0228]
The respective images were output to the samples 101 to 103 (samples frozen and stored at 50 ° C. and 40% RH) of Example 1 by the exposure apparatus used in Example 1, and the developing start solution and the development after running processing were performed. The developing process was carried out in the same manner as in Example 1 with the liquid.
[0229]
Next, the ΔGOF value of the color patch portion was measured in the same manner as in Example 1, and the obtained results are shown in Table 4.
[0230]
[Table 4]

[0231]
It was confirmed that the effect of the present invention was obtained, although the result was slightly shifted due to the influence of different image data.
[0232]
Next, when the same image is read with pixels of one side of 150 μm and converted into data of pixels of one side of 10 μm, an image having a colorless (white) edge of 10 μm and having a constant density inside is obtained. Converted to data. This data was subjected to RIP processing, and this image was output to the samples 101 to 103 of Example 1 (frozen storage and 50 ° C. 40% storage samples) by the exposure apparatus used in Example 1, and the developing start solution and the running processing were used. Each process was performed with a developer to obtain a color image.
[0233]
For this image, the ΔGOF value of the color patch portion was measured in the same manner as in Example 1, and the obtained results are shown in Table 5.
[0234]
[Table 5]

[0235]
This image is an image having a fine network structure, but is basically a density-modulated image. Comparing the results in Table 5 with the results in Table 4, it can be seen that the change in hue is smaller in the case of creating a density modulated image.
[0236]
In addition, looking at the difference in image quality between the natural image and the portrait in the two output methods, it was confirmed that the image created by density modulation is particularly excellent in smooth reproduction of portrait skin.
[0237]
Example 4
In the evaluation of the first embodiment, a printing condition profile in which the exposure apparatus associates digital image information with device-independent image data and an exposure condition profile in which the device-independent image data and exposure image data are associated with each other Based on the above, in the same manner except that a color conversion means for converting the digital image information into the exposure digital image data is provided, using the samples 101 to 103, the ΔGOF value is measured, and the obtained result is obtained. The results are shown in Table 6.
[0238]
[Table 6]

[0239]
As is evident from Table 6, by preparing an exposure condition profile for the sample before storage, the hue deviation of the sample stored frozen was greatly improved even in the comparative sample, but the sample was stored at 50 ° C. and 40%. In the case of the sample, the hue shift was not improved but rather increased. On the other hand, in the sample of the present invention, the hue deviation was smaller after storage at 50 ° C. and 40%, not to mention improvement by the frozen storage sample. In the present invention, application of such a color management system is a more preferable embodiment.
[0240]
Table 7 shows the results of the same evaluation as described above performed on the density-modulated image having a fine network structure of Example 3.
[0241]
[Table 7]

[0242]
As is clear from Table 7, the hue shift is significantly improved in the comparative sample as in the area-modulated image, but the sample of the present invention shows more excellent characteristics.
[0243]
Example 5
Except that the color developing agent N-ethyl-N- (β-hydroxyethyl) -4-aminoaniline sulfate used in the color developing solution described in Example 1 was changed to equimolar exemplified compound CD-6. Similarly, using the samples 101 to 103, the ΔGOF value was measured, and the obtained results are shown in Table 8.
[0244]
[Table 8]

[0245]
As is clear from Table 8, the effect of the present invention can be obtained in a system using a color developing solution containing Exemplified Compound CD-6 in the same manner as in the above Examples. In addition, as compared with the results in Table 2, it was found that a more stable sample can be obtained with the color developer using CD-6 even after storage.
[0246]
【The invention's effect】
According to the present invention, a proof image having a small hue change before and after continuous development processing due to a change in the halftone dot percentage of the secondary color can be stably formed regardless of the storage state of the silver halide photosensitive material.
[Brief description of the drawings]
FIG. 1 is a flowchart of a processing operation for editing image data into exposure data according to the present invention.
FIG. 2 is a block diagram showing a processing operation of the present invention.

Claims (7)

A silver halide light-sensitive material having at least one yellow image forming unit, magenta image forming unit, and cyan image forming unit on a support has a resolution of 1000 dpi (dots per 2.54 cm) or more. In a color image forming method by area modulation in which an image is exposed by an exposure device capable of changing image density and then developed with a color developing solution containing a color developing agent, the yellow image forming unit is represented by the following general formula (I). The magenta image forming unit contains a compound represented by the following general formula (II), and the cyan image forming unit contains the compound represented by the following general formula (III), general formula (IV), or general formula (V) ) And a compound selected from the general formula (VI).

[Wherein, R ₁₁ represents an alkyl group having 3 or less carbon atoms or a diffusion-resistant group, and Y ₁ represents a diffusion-resistant group when R ₁₁ represents an alkyl group having 3 or less carbon atoms, and R ₁₁ represents a diffusion-resistant group. When it represents a group, it represents a hydrogen atom. Z ₁ represents a group which is released by a reaction with an oxidized form of a developing agent bonded via a nitrogen atom. ]

[Wherein, R ₂₁ represents a primary or secondary alkyl group, an arylamino group, or an alkoxy group, R ₂₂ represents a linear linking group having 3 or more carbon atoms, and J ₂ represents-(C = O ) -, - (O = S = O) -, - (C = O) -O -, - O- (C = O) -, - (C = O) -NR 24 -, - Ph- (C = _{O) -NR 24 -, - NR} 25 - (C = O) -, - Ph-NR 25 - (C = O) -, - (O = S = O) -NR 26 -, - Ph- (O = _{S = O) -NR 26 -,} - NR 27 - (O = S = O) - or _{Ph-NR 27 - (O =} S = O) - _represents, R 24 _{to R 27} are each a hydrogen atom, an alkyl Represents a group, a cycloalkyl group, an alkenyl group, an alkynyl group or an aryl group, and Ph represents a phenylene group. R ₂₃ represents a non-diffusible group, and X ₂ represents a group capable of leaving by reaction with an oxidized form of a color developing agent. ]

[In the formula, Ar is an aryl group or a heterocyclic group, R ₁ is an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, L is a divalent linking group, n represents 0 or 1, and Cp represents It is represented by the following general formula (A) or general formula (B).

Wherein, X represents a hydrogen atom, oxidation of a halogen atom or a color developing agent and the coupling and desorption radicals, R _M represents a monovalent substituent. ]

[Wherein, R ₂ , R ₃ and R ₄ each represent an alkyl group, alkenyl group, alkynyl group, aryl group or heterocyclic group, L represents a divalent linking group, n represents 0 or 1, and Cp represents the above general formula. It has the same meaning as Cp in formula (III). ]

[Wherein, R ₅ represents an unsubstituted alkyl group, alkenyl group or alkynyl group having 5 or more carbon atoms, R ₆ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group; ₇ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, J ₁ represents —O— or —NR ₁₁ —, and R ₁₁ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group. L represents a divalent linking group, n represents 0 or 1, and Cp has the same meaning as Cp in formula (III). ]

[Wherein, R ₈ , R ₉ and R ₁₀ each represent an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, L represents a divalent linking group, and W represents —CO— or —SO ₂ —. And Cp has the same meaning as Cp in formula (III). ] A silver halide photosensitive material having at least one yellow image forming unit, magenta image forming unit, and cyan image forming unit on a support is exposed by an exposure device having a resolution of 1000 dpi or more and capable of changing the image density. After that, in a color image forming method by area modulation in which development processing is carried out with a color developing solution containing a color developing agent, the yellow image forming unit comprises a compound represented by the general formula (I) and a phosphate or phosphine oxide compound. Wherein the magenta image forming unit contains a compound represented by the general formula (II), an alcohol compound having 10 or more carbon atoms and a phosphate or phosphine oxide compound, and the cyan image forming unit contains The compound represented by the general formula (III) has a relative dielectric constant of 6 or more. Color image forming method characterized by containing the point organic solvent. A silver halide photosensitive material having at least one yellow image forming unit, magenta image forming unit, and cyan image forming unit on a support is exposed by an exposure device having a resolution of 1000 dpi or more and capable of changing the image density. A color image forming method based on area modulation in which a development process is performed with a color developing solution containing a color developing agent, wherein a density-modulated image is output as an image in which a specific pattern is superimposed on an original image. . The yellow image forming unit contains the compound represented by the general formula (I), the magenta image forming unit contains the compound represented by the general formula (II), and the cyan image forming unit contains the compound represented by the general formula (II). The color image forming method according to claim 3, comprising a compound represented by (III). The exposure apparatus, based on a print condition profile that associates digital image information with device-independent image data, and an exposure condition profile that associates device-independent image data with exposure digital image data, 5. A color image forming method according to claim 1, further comprising a color conversion unit for converting image information into the digital image data for exposure. The color developing agent is 4-amino-3-methyl-N-ethyl-N- (β- (methanesulfonamido) ethyl) aniline, according to any one of claims 1 to 3, wherein Color image forming method. After exposing a silver halide photosensitive material having at least one yellow image forming unit, magenta image forming unit, and cyan image forming unit on a support by an exposure device having a resolution of 1000 dpi or more and capable of changing the image density, In a color image forming method by area modulation for development, the relationship between the amount of exposure to a silver halide photosensitive material and the amount corresponding to the amount of image dye and the relationship between the pixel color and the amount corresponding to the amount of image dye are used. 7. The color image forming method according to claim 1, wherein energy required for image formation is obtained by performing the calculation.

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